WO2018034549A1 - Catalyst composition for preparing polyketone compound, palladium mixed catalyst system, method for preparing polyketone compound using same, and polyketone polymer - Google Patents

Abstract

The present invention relates to a catalyst composition for preparing a polyketone compound, the catalyst composition comprising: an onium salt compound having 5 to 40 carbon atoms and comprising a carboxylic acid group or a carrier surface-modified with a sulfonic acid group; and a palladium-based catalyst. Through the catalyst composition, the present invention can provide: a palladium mixed catalyst system capable of showing high activity and preventing fouling in the preparation of polyketone; a method for preparing a polyketone compound, the method being capable of preventing fouling, skipping the feeding of seeds, and attaining excellent stability and activity in a polymerization reaction, by using the palladium mixed catalyst system; and a polyketone polymer with a high apparent density prepared from the method.

Description

Catalyst composition for producing polyketone compound, palladium mixed catalyst system, polyketone compound production method and polyketone polymer using same

The present invention relates to a palladium mixed catalyst system capable of preventing fouling while showing high activity in polyketone production, a method for preparing a polyketone compound using the mixed catalyst system, and a polyketone polymer prepared therefrom.

Polyketones are polymers also known as carbon monoxide / olefin copolymers. Recently, polyketone is being actively used as a raw material such as high-strength fibers and engineering plastics, and demand is increasing. The synthesis of such polyketones has excellent industrial applicability in terms of converting carbon monoxide into useful materials and providing polymer compounds having excellent physical properties.

In the conventional polyketone production method, the catalyst is dissolved in methanol and then introduced into a reactor to polymerize carbon monoxide and ethylene to polyketone under pressure. In the conventional polyketone production method, the polymerization reaction proceeds in a homogeneous state dissolved in methanol, and as a result, polyketone (copolymer of carbon monoxide and ethylene) in the form of an amorphous slurry having no solubility in the solvent is formed.

However, the polyketone prepared in the form of a conventional amorphous slurry has a low apparent density because the particle shape is not controlled, and there is a problem of low productivity per unit volume of the reactor. Such polyketone particles in the form of amorphous slurry are attached to the reactor surface, the stirring device and the conveying piping, causing fouling problems in the mass production process.

In addition, the conventional polyketone manufacturing method is difficult to increase the activity to the level of industrial usefulness without using additives such as sulfonic acid (sulfonic acid) directly, but the problem that fouling occurs easily when using a strong acid additive There is a difficulty in applying to the mass production process.

Therefore, there is an increasing demand for a method for producing polyketone, which is capable of controlling particle shape and preventing fouling occurring during a polymerization reaction and at the same time increasing reaction activity to an industrially useful level.

One object of the present invention is to uniformly control the shape and size of the finally produced polyketone, thereby improving the apparent density, to prevent fouling during the process, and to improve the stability and activity of the polymerization reaction It is to provide a catalyst composition which can be improved.

Another object of the present invention is to provide a palladium mixed catalyst system capable of preventing fouling while showing high activity in polyketone production by using an onium salt compound substituted with carboxylic acid as an additive.

Still another object of the present invention is to prevent fouling by using the catalyst composition and the palladium mixed catalyst system described above, omission of seed can be omitted, and a method for producing a polyketone compound having excellent stability and activity during a polymerization reaction, and It is to provide a polyketone polymer of apparent high density prepared therefrom.

The above and other objects of the present invention can be achieved by the present invention described below.

One embodiment of the present invention is an onium salt compound having 5 to 40 carbon atoms containing a carrier or a carboxylic acid surface-modified sulfonic acid group; And palladium-based catalysts; It relates to a catalyst composition for producing a polyketone compound comprising a.

Another embodiment of the present invention relates to a palladium mixed catalyst system for producing a polyketone compound including the above-described catalyst composition for producing a polyketone compound and using olefin and carbon monoxide as reactants.

Another embodiment of the present invention relates to a polyketone production method comprising the step of dispersing a catalyst composition for preparing a polyketone compound in a solvent and adding olefin and carbon monoxide to the dispersed catalyst composition.

Another embodiment of the present invention relates to a polyketone polymer formed by a polyketone production method and having an apparent density of 0.1 to 0.5 g / ml.

The present invention can provide a catalyst composition capable of preventing fouling while showing high activity in polyketone production, and a palladium mixed catalyst system including the same, and can prevent fouling using the mixed catalyst system, It is possible to control the shape and size of the polyketone, omission of seed input, it is possible to provide a method for producing a polyketone compound having excellent stability and activity during the polymerization reaction and the apparent high density polyketone polymer prepared therefrom.

1 is a SEM photograph of a carrier surface-modified with a sulfonic acid group prepared in Preparation Example 1.

FIG. 2 is a SEM photograph of a carrier surface-modified with the sulfonic acid group of Preparation Example 1, which was collected after the polymerization reaction of Example 1.

3 is an electron micrograph of the carrier surface-modified with the sulfonic acid group prepared in Preparation Example 2.

4 is a SEM photograph comparing (a) and (b) before (a) and after applying a carrier modified with a sulfonic acid group prepared in Preparation Example 2 to prepare a polyketone of Example 3.

5 is a photograph of the polyketone prepared in Example 1.

6 is a photograph of the polyketone prepared in Example 3.

7 is a photograph of the polyketone prepared in Example 4.

8 is a photograph of the polyketone prepared in Comparative Example 2.

9 is a photograph of the polyketone prepared in Comparative Example 4.

10 shows a carrier 100 surface-modified with a sulfonic acid group of the first embodiment of the present invention.

11 shows a carrier 200 surface-modified with a sulfonic acid group of the second embodiment of the present invention.

Catalyst composition

One embodiment of the present invention is an onium salt compound having 5 to 40 carbon atoms containing a carrier or a carboxylic acid surface-modified sulfonic acid group; And palladium-based catalysts; It relates to a catalyst composition for producing a polyketone compound comprising a.

Through this, the present invention can provide a catalyst composition and a palladium mixed catalyst system including the same, which exhibits high activity in polyketone production and can prevent fouling, and prevents fouling by using the mixed catalyst system. And it is possible to omit the seed input, it is possible to provide a method for producing a polyketone compound excellent in stability and activity during the polymerization reaction and the apparent high density polyketone polymer prepared therefrom.

In particular, the catalyst composition for producing a polyketone compound of the present invention and a palladium mixed catalyst system using the same can prevent fouling generated in the conventional catalyst system for producing polyketone and at the same time increase the reaction activity to an excellent level, and add a separate seed. In a seed non-injection method which does not, a polyketone polymer having excellent apparent density can be prepared.

( Sulfonic acid group Surface modified carrier )

The carrier surface-modified with the sulfonic acid group is included as a hetero material for a palladium-based catalyst. As used herein, the term “hetero material” refers to a material included as a component included in a catalyst composition as a mixture with a palladium-based catalyst.

In this case, the surface-modified carrier of the sulfonic acid group of the present invention; And a palladium-based catalyst; the catalyst composition in a mixed form has, for example, a state different from a catalyst in which a palladium-based catalyst is supported on a surface modified with a sulfonic acid group, and is applied to a polyketone polymerization process. The shape and size of the final polyketone can be uniformly controlled, thereby improving the apparent density of the polyketone, preventing fouling during the process, and improving the stability and activity of the polymerization reaction. have.

The equivalent ratio of the surface-modified carrier and the palladium-based catalyst in the catalyst composition may be 1: 0.1 to 1:10, specifically 1: 0.1 to 1: 2. More specifically, the equivalent ratio may be 1: 0.1 to 1: 1.2. It is possible to obtain higher catalyst activity and apparent density of a high polyketone polymer without fouling during polyketone polymerization using the catalyst composition in the above range.

The carrier surface-modified with the sulfonic acid group in the catalyst composition and the palladium-based catalyst may be included in a dispersed form in a solvent. Specifically, the solvent may be an alcohol solvent, more specifically an alcohol compound having 1 to 20 carbon atoms, for example methanol. When the catalyst composition is applied to polyketone polymerization, the reaction activity may be further improved, and the boiling point may be advantageous for the post-treatment process.

The surface-modified carrier with the sulfonic acid group can uniformly control the shape and size of the polyketone to be polymerized, prevent fouling during the polymerization reaction, and serve to further improve the apparent density of the polyketone particles formed.

In particular, the sulfonic acid group of the carrier surface-modified with the sulfonic acid group interacts with the palladium-based catalyst during the polymerization reaction to more effectively prevent fouling, and to form a polyketone in powder form having a high apparent density, There is no adverse effect on the activity, and the effect of maintaining high catalytic activity is excellent.

Specifically, the carrier surface-modified by the sulfonic acid group may include a structure in which a functional group represented by any one of the following Formulas 1-1 to 1-3 is bonded to the surface of the carrier.

[Formula 1-1]

* -SO ₃ H

In Chemical Formula 1-1, * means a portion bonded to the carrier surface.

[Formula 1-2]

In Formula 1-2, R ²¹ to R ²⁶ are each independently hydrogen or alkyl of C1 to C20; * Means the part bonded to the surface of the carrier.

[Formula 1-3]

In Formula 1-3, R ³¹ to R ³⁴ are each independently hydrogen or alkyl of C1 to C20; * Denotes the part that is bonded to the carrier surface. it means.

Specifically, * in Chemical Formulas 1-1 to 1-3 may be a bonding site connected to the surface of the carrier to form a C-C bond or a Si-C bond. In this case, the carrier and the functional group represented by any one of Formulas 1-1 to 1-3 may be linked to a C-C bond or Si-C bond having excellent binding strength, and thus may have high stability and improved fixing force to the carrier.

The carrier is a porous particle containing pores, it is possible to control the surface area, pore radius, pore, volume, etc. of the polyketone during the polymerization reaction.

The carrier may be silica, zeolite, graphite, carbon black, graphene, carbon nanotube, activated carbon, polystyrene, microporous organic network, metal organic structure (MOF), zeolite-like structure (ZIF), organic skeleton It may comprise one or more of a biopolymer including a structure (COF) and cellulose. In this case, the effect of preventing fouling can be further improved while uniformly controlling the shape and size of the polyketone during the polymerization reaction, and excellent handling properties of the catalyst composition and the polyketone prepared therefrom, It may have more advantageous properties.

Specifically, the carrier may include one or more of silica, zeolite-like structures, polystyrene, and microporous organic network polymers. In this case, the effect of preventing fouling can be further improved while controlling the shape and size of the polyketone, and commercial usability can be further increased.

When using a microporous organic network polymer (microporous organic network) as the carrier, the kind thereof is not particularly limited. For example, Sonogashira coupling reaction, Suzuki coupling reaction or other known cross-coupling using a compound comprising two or more triple bonds at the end and / or a compound comprising a leaving group at the end. It may be an organic network polymer formed by the reaction.

The leaving group may be used in the Sonogashira coupling reaction, Suzuki coupling reaction or other known cross coupling reaction, but is not limited thereto. Specifically, the leaving group (X) is halogen, tosylate, triflate, mesylate, mesylate, boronic acid, boronic ester, -N ^{2 +} X ^- may be a living group available for the coupling reaction, or the like. For example, the compound including the leaving group may be a dinitrogen compound (RN ²⁺ ), a dialkyl ether compound (R-OR ₂ ⁺ ), a triflate compound (R-OSO ₂ R ^F ), a tosylate compound (R -OTf), halides (R-Cl, R-Br, RI, RF), mesylate compounds (R-OMs), nitrate compounds (R-ONO ₂ ), phosphate compounds (R-OPO (OH) ₂ ) , A thioether compound (R-SR ₂ ⁺ ), a carboxylate compound (R-OCOR), and also a compound containing two or more leaving groups, RN ₂ X, R-OSO ₂ R, R-OSO ₂ F, SO _{2 -R, SOR, R-SR} , IPhX, IROTf, I (OH) OTs, RCOCl, R-SO 2 -Cl, RN 2+ X -, R-OSO 2 CF 3, R-OSO 2 -Rf, R -OSO ₂ CH ₃ , Ar-Ar-I ⁺ , R-OPO (OR) ₂ , PF ^6- , RB (OR) ₂ , R ₂ NH, RX, RCO (SEt), RCO (SEt) Ar-SMe, RC≡CH, Ar—N ₂ X, R (C═O) R ₂ , R-HC═O, R-HC═O and the like.

Rf is perfluoroalkyl, Tf is triflate, Ms is mesylate, X is halogen, R is substituted or unsubstituted hydrocarbon having 1 to 20 carbon atoms, Ar is aromatic hydrocarbon having 6 to 20 carbon atoms.

In one embodiment, the compound including a leaving group may be a compound represented by the following formula (A).

[Formula A]

(XR ¹⁰ ) _p (Z)

In Formula A, R ¹⁰ is an alkylene group having 1 to 20 carbon atoms or an arylene group having 1 to 20 carbon atoms, and each X is independently an ethyne group, a halogen group, a boronic acid group, a boronic acid ester group, and a triflate group. Z is a carbon atom, a nitrogen atom or a hydrocarbon having 3 to 10 carbon atoms, and p is 2 to 6 carbon atoms.

For example, the compounds may be in the form of a skeleton structure of each of the formulas A1 to A4.

[Formula A1]

[Formula A2]

[Formula A3]

[Formula A4]

In Formulas A1 to A4, each X is independently an ethyne group, a halogen group, a boronic acid group, a boronic acid ester group, a triflate group, and Z is a carbon atom, a nitrogen atom, or a hydrocarbon having 3 to 10 carbon atoms. In this case, the hydrocarbon having 3 to 10 carbon atoms may be a cyclic hydrocarbon or a hydrocarbon having a three-dimensional structure. For example, in Example A4, Z may be an adamantane structure to which 4 is linked.

In addition, for example, when the compounds of Formulas A1 and A2 are used as reactants, supply and demand of raw materials is easy, and the unit cost is low, and when applied to a large scale mass production process, economical efficiency may be improved.

Specifically, the carrier may have an average particle diameter of 0.01 μm to 5 μm. More specifically, it may be 0.05 μm to 2 μm, 0.45 μm to 1.8 μm. Within this range, the shape and size of the polyketone can be more uniformly controlled and the apparent density can be improved. The average particle diameter of the carrier can be adjusted according to, for example, the shape and size of the desired polyketone particles.

Specifically, the carrier may be a surface area of 5 m ² / g to 2000m ² / g. More specifically, it may be 20 m ² / g to 1800m ² / g, 30 m ² / g to 1700m ² / g or 30 m ² / g to 900m ² / g. Within this range, the shape and size of the polyketone can be more uniformly controlled and the apparent density can be improved. The surface area of the carrier can be adjusted according to, for example, the shape and size of the desired polyketone particles.

Specifically, the carrier may have an average pore radius of 0.1 nm to 25 nm. More specifically, it may be 0.5 nm to 10 nm, or 1 nm to 6 nm. Within this range, the shape and size of the polyketone can be more uniformly controlled and the apparent density can be improved. The average pore radius of the carrier can be adjusted, for example, according to the shape and size of the desired polyketone particles.

Specifically, the carrier may have a pore volume of 0.01 mL / g to 1.0 mL / g. More specifically, it may be 0.02 mL / g to 0.7 mL / g, or 0.04 mL / g to 0.5 mL / g. Within this range, the shape and size of the polyketone can be more uniformly controlled and the apparent density can be improved. The average pore volume of the carrier can be adjusted, for example, according to the shape and size of the desired polyketone particles.

In particular, the carrier may comprise an aromatic ring in the structure. In this case, the stability of the carrier is excellent, and when the surface is modified with sulfonic acid, it is possible to realize excellent surface modification efficiency.

In a first embodiment, the carrier surface-modified with a sulfonic acid group may be a hollow structure including a microporous organic network polymer having a repeating unit represented by the following Chemical Formula 1-4.

[Formula 1-4]

In Formula 1-4, A is a linking portion of an atom.

The carrier 100 surface-modified with the sulfonic acid group of the first embodiment is exemplarily illustrated in FIG. 10. Referring to FIG. 10, the carrier 100 surface-modified with the sulfonic acid group of the first embodiment is a hollow structure 101 formed of a hollow structure in which the interior 102 is empty, and the hollow structure 101 is represented by the above formula. It may be formed of a microporous organic network polymer having a repeating unit represented by 1-4. For example, the hollow structure 101 is connected to A of one repeating unit represented by Formula 1-4 with A of another repeating unit represented by Formula 1-4 in a single bond to form an organic network. It contains microporous inside.

In addition, the hollow structure 101 of FIG. 10 may use a zeolite-like structure as a template for allowing the microporous organic network polymer having a repeating unit represented by Chemical Formula 1-4 to have a hollow structure. In this case, the carrier 100 surface-modified with sulfonic acid group may include a microporous organic network polymer and a zeolite-like structure as a carrier. In addition, the zeolite-like structure used as the template may be used in a state of being removed through an etching process.

In FIG. 10, the structure of the hollow structure 101 is represented by a spherical shape for convenience of expression, but the shape thereof is not limited as long as it includes the hollow structure. For example, the hollow structure 101 may have an internal structure. It may include the shape of an empty polyhedron.

In a second embodiment, the carrier surface-modified by the sulfonic acid group includes a microporous organic network polymer layer having a silica carrier and a repeating unit represented by the following Chemical Formula 1-5 formed on the surface of the silica carrier. Can be.

[Formula 1-5]

In Formula 1-5, each A ′ independently represents a linking site or a linking site between repeating units of an atom to be bonded to a carrier, and at least one of A ′ is a linking site of atoms to be bonded to a carrier, and at least At least one is the link between repeat units.

11 shows a carrier 200 surface-modified with the sulfonic acid group of the second embodiment. Referring to FIG. 11, the carrier 200 surface-modified with the sulfonic acid group of the second embodiment includes a silica carrier 202 and a microporous organic network polymer layer 201 formed on the surface of the silica carrier. The microporous organic network polymer layer 201 is formed of a microporous organic network polymer having a repeating unit represented by Chemical Formula 1-5, and a carrier 200 surface-modified with the sulfonic acid group of the second embodiment. ) May be a form in which the inside of the microporous organic network polymer layer 201 is filled with the silica carrier 202. For example, the microporous organic network polymer layer 201 includes a polymer having a repeating unit represented by Formula 1-5, wherein at least one A 'of one repeating unit is single with A' of an adjacent repeating unit. Are bonded to form an organic network, and at least one A ′ forms an Si—C bond with the silica carrier 202.

In addition, the microporous organic network polymer layer 201 of FIG. 11 uses silica as a template, and the microporous organic network polymer layer 201 having a repeating unit represented by Chemical Formula 1-5 is a silica carrier. It may be formed on the surface of the (202). In this case, the carrier 200 surface-modified with sulfonic acid groups may include a microporous organic network polymer and silica as a carrier.

In FIG. 11, the structure of the silica carrier 202 is expressed as a spherical structure for convenience of expression, but the shape thereof is not limited thereto and may include, for example, a polyhedron shape.

In a third embodiment, the carrier surface-modified by the sulfonic acid group may include a polystyrene compound having a repeating unit represented by the following Chemical Formula 1-6.

[Formula 1-6]

In Chemical Formula 1-6, R ⁶ is a sulfonic acid group, a para-toluenesulfonic acid group, or a benzene sulfonic acid group, and n is 10 to 20,000.

In such a case, the catalyst composition can further improve the apparent density and uniformity while further miniaturizing the particles of the finally produced polyketone.

In addition, the polystyrene compound may be a copolymer including the repeating unit represented by Chemical Formula 1-6. For example, the polystyrene compound may be a copolymer of the repeating unit of Formula 1-6 and divinylbenzene.

In a fourth embodiment, the carrier surface-modified by the sulfonic acid group may have a structure in which a functional group represented by any one of the above-described formulas 1-2 and 1-3 is Si-C bonded. In this case, the stability of the catalyst composition may be further improved and the effect of preventing fouling may be better.

The carrier surface-modified by the sulfonic acid group may be prepared by adding sulfuric acid or chlorosulfuric acid to the carrier, for example, the surface-modified carrier.

Producing a carrier surface-modified with a sulfonic acid group may include preparing a carrier and sulfonating the surface of the carrier to surface-modify the sulfonic acid group.

The carrier may be silica, zeolite, graphite, carbon black, graphene, carbon nanotube, activated carbon, polystyrene, microporous organic network, metal organic structure (MOF), zeolite-like structure (ZIF) as described above. ), Organic framework (COF) and may include one or more of the biopolymer (biopolymer) including cellulose. The carrier may be used or manufactured by using a commercially available product. In this case, the effect of preventing fouling can be further improved while uniformly controlling the shape and size of the polyketone during the polymerization reaction, and the handleability of the catalyst composition and the polyketone prepared therefrom can be further improved.

Specifically, the carrier may include one or more of silica, zeolite-like structures, polystyrene, and microporous organic network polymers. In this case, while controlling the shape and size of the polyketone, the effect of preventing fouling can be further improved, and the economic effect is also better.

Specifically, preparing the carrier may include reacting the prepared carrier with a compound represented by the following Formula 5 or 6 after preparing the carrier. Through this, by forming a structure containing an aromatic ring on the surface of the carrier to further improve the efficiency of the surface is modified to the sulfonic acid group, it is possible to further increase the binding strength of the sulfonic acid and the carrier.

[Formula 5]

Ar-X ₂

[Formula 6]

Ar-Mg-X

In Formulas 5 to 6, Ar is benzyl or phenyl, Mg is magnesium, X is halogen.

Specifically, the halogen in Formula 5 to Formula 6 may be, for example, Cl, Br, F or I, more specifically I, Cl or Br. In this case, supply and demand of the raw materials is easy and economical, the reaction rate can be further improved.

In one embodiment, the step of preparing a carrier is reacting a zeolite-like structure with tetra- (4-ethynylphenyl) -methane as a template and the compound of Formula 1-6 under Pd (PPh ₃ ) ₂ Cl ₂ and CuI catalyst The carrier can be prepared by the method. In this case, the prepared carrier is subjected to sulfonation of a surface to provide a carrier modified with sulfonic acid, which is a hollow structure including a microporous organic network polymer having a repeating unit represented by Chemical Formula 1-4. can do.

In another embodiment, the preparing of the carrier may be performed by reacting silica with tetra- (4-ethynylphenyl) -methane as a template and the compound of Chemical Formula 1-6 under Pd (PPh ₃ ) ₂ Cl ₂ and CuI catalyst. Carriers can be prepared. In this case, the carrier prepared is a sulfonic acid including a microporous organic network polymer layer having a silica carrier and a repeating unit represented by Formula 1-5 described above formed on the surface of the silica carrier through sulfonation of the surface. A surface modified carrier can be provided.

In another embodiment, the preparing of the carrier may include dispersing the dehydrated carrier in a solvent and then adding the compound represented by Chemical Formula 5 and reacting the same to bind an aromatic functional group to the surface of the carrier. In this case, the surface modification efficiency and carrier stability in the sulfonation step can be further improved.

Specifically, the dehydration treatment of the carrier may be performed by supplying nitrogen gas or argon gas at 600 ° C. to 900 ° C. using a heating furnace.

Specifically, the solvent in which the dehydrated carrier is dispersed may be an ether solvent, more specifically an alkyl ether solvent, and may be, for example, a diethyl ether solvent. In this case, the dispersibility can be further improved.

For example, when the carrier is silica and Ar is benzyl in Chemical Formula 5, the carrier prepared is sulfonated on a surface thereof to which the silica carrier and the functional group represented by Chemical Formula 1-2 are bonded to Si-C. A carrier modified with a sulfonic acid group having a structure can be provided.

For example, when the carrier is silica and Ar is phenyl in Formula 5, the prepared carrier is sulfonated on the surface to which the silica carrier and the functional group represented by Formula 1-3 are bonded to Si-C. A carrier modified with a sulfonic acid group having a structure can be provided.

Sulfonation of the surface of the carrier to surface-modify the sulfonic acid group may include sulfonation (sulfonation) by adding sulfuric acid or chlorosulfuric acid to the prepared carrier.

In detail, the surface modification may be performed by treating sulfuric acid (95%) or chlorosulfuric acid on the prepared carrier to induce a sulfonation reaction on the benzene ring in the structure of the carrier. Through this, each carrier described above is modified with a functional group having a structure including a sulfonic acid group in the terminal benzene ring.

In this way, when the carrier whose surface is modified by the sulfonic acid group is produced, the conversion rate (surface modification rate) of the carrier by sulfonation is very excellent. In addition, even under extreme reaction conditions of treating concentrated sulfuric acid or chlorosulfuric acid, the formed C-C bonds or Si-C bonds are not broken, so that most of the functional groups are immobilized on the surface of the carrier.

In one embodiment, sulfonation of the carrier may be carried out by the reaction of Scheme 1 below.

Scheme 1

In another embodiment, aromatic sulfonation of the carrier can be carried out by the reaction of Scheme 2 or Scheme 3 below.

Scheme 2

Scheme 3

For example, compared to a method of immobilizing an organic material with a hydroxyl group (≡Si-OH) on a silica surface and immobilizing it through a Si—O bond, after attaching an aromatic ring to a carrier as in Schemes 2 to 3, When the surface is modified by sulfonation, the bonding force between the surface modifier and the carrier surface is more excellent. In this case, there is an advantage that the surface modifier is not easily leached. Therefore, the surface-modified carrier prepared by the sulfonic acid group prepared by such a manufacturing method is very excellent in stability and may help to realize high activity in the polymerization reaction.

Specifically, the carrier surface-modified with a sulfonic acid group may include a sulfonic acid group as 0.1 mmol-H ⁺ / g to 3 mmol-H ⁺ / g. In this case, the efficiency of the polyketone synthesis process by the sulfonic acid group can be further improved.

( Carboxylic acid groups  Containing Onium salt  compound)

When the onium salt compound including the carboxylic acid group is applied to the polyketone production method, it is possible to more effectively prevent fouling by lowering the reaction rate smoothly throughout the polymerization reaction. The onium salt compound containing a carboxylic acid group serves to allow the palladium mixed catalyst system for producing polyketone of the present invention to implement a reaction mode different from the rapid increase in the initial reaction rate of polymerization occurring in the conventional catalyst system for producing polyketone. do.

The polyketone production method of the present invention using the catalyst composition for producing polyketone and the palladium mixed catalyst system omits the process of controlling the pressure, temperature, solvent, reaction time, reaction rate, and the like in the middle of the polymerization reaction. At the same time it can prevent fouling and achieve good activity. This property offers advantageous advantages for applications in mass production processes.

In addition, the salt of the onium salt compound containing the carboxylic acid group may interact with the palladium catalyst used for the polyketone polymerization to form a heterogeneous seed which is very small in size, and may be formed around the catalyst. The shape of the polyketone polymer being synthesized can be controlled.

Specifically, the onium salt compound including the carboxylic acid group is a carboxylic acid group substituted with the onium salt compound, the onium salt compound is at least one of a pnictogen element, a chalcogen element, and a halogen element It may include, for example, may be ammonium, oxonium, phosphonium, sulfonium compound and the like.

More specifically, the onium salt compound including the carboxylic acid group may be represented by the following Formula 2-1.

[Formula 2]

[Z-COOH] ⁺ [X] ^-

In Formula 2, Z is a hydrocarbon group having 1 to 20 carbon atoms containing nitrogen, phosphorus or sulfur; [X] ^- is an anion (anion) containing a halogen, oxygen, boron, phosphorous, sulfur, or a combination thereof.

When the compound of Formula 2 is used as an onium salt compound containing a carboxylic acid group, the effect of preventing fouling while enhancing the reaction activity and increasing the apparent density of the polyketone compound prepared without adding a separate seed is further increased. Can be improved.

The hydrocarbon group of 1 to 20 carbon atoms is not particularly limited, but for example, an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 1 to 20 carbon atoms, a heteroalkyl group of 1 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, and 3 carbon atoms. To 20 heteroaryl groups and the like. In this case, not only the supply and demand of the raw materials can be easily provided, but also the effect of increasing the reaction activity while preventing fouling and increasing the apparent density of the polyketone compound prepared without adding a separate seed can be further improved.

In an embodiment, in Chemical Formula 2, Z may be an aromatic hetero ring group containing nitrogen, phosphorus, or sulfur, or a branched hetero alkyl group containing nitrogen, phosphorus, or sulfur.

In addition, the hydrocarbon group having 1 to 20 carbon atoms may be independently substituted or unsubstituted, wherein the substituent may be, for example, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen group. have.

In Formula 2, [X] ^- it is an anion (anion) containing bonded to the onium ion substituted with a carboxylic acid available halogen, oxygen, boron, phosphorous, sulfur, or a combination thereof.

Specifically, [X] ^-, for example, a halogen anion, including chloride, bromide or anions of iodine; Oxy anions including borate, sulfonate, carbonate, nitrate, sulfate, nitrite, phosphate, phosphite, sulfite, tosylate and the like; Anions containing boron atoms; Anions containing phosphorus atoms; Or tetrafluoroborate anion, tetraarylborate anion (aryl group is pentafluorophenyl (Ar = C ₆ F ₅ )), sulfonic acid anion, para-toluenesulfonic acid anion, trifluoroacetic anion, trifluoromethanesulphate as acid anion, hexafluorophosphate _{^{anion, ClO 4 -, ClO 3 -}} , ClO 2 -, ClO -, BrO 4 -, BrO 3 -, BrO 2 -, BrO -, IO 4 -, IO 3 -, IO 2 - Anions including two or more of halogen, oxygen, boron, phosphorus and sulfur, including anions such as, IO ⁻ , CO ₃ ^2- and the like; And the like.

In addition, the anion including the halogen, oxygen, boron, phosphorus, sulfur or a combination thereof may be independently substituted or unsubstituted, wherein the substituent is, for example, an alkyl group having 1 to 10 carbon atoms , An aryl group having 6 to 20 carbon atoms, a halogen group, or the like.

The compound of Formula 2 is, for example, glycine betaine hydrochloride (glycine betaine hydrochloride), trigonelline hydrochloride (trigonelline hydrochloride), 3- (carboxymethyl) -1-methyl-1H-imidazol-3-ium Bromide (3- (carboxymethyl) -1-mesityl-1H-imidazol-3-ium bromide), 3- (carboxymethyl) -1- (2,6-diisopropylphenyl) -1H-imidazol-3-ium Bromide (3- (carboxymethyl) -1- (2,6-diisopropylphenyl) -1H-imidazol-3-ium bromide), 3- (carboxymethyl) -1-methyl-1H-imidazol-3-ium bromide (3 -(carboxymethyl) -1-methyl-1H-imidazol-3-ium bromide), 3- (carboxymethyl) -1-methyl-1H-benzo [d] imidazol-3-ium bromide (3- (carboxymethyl)- 1-methyl-1H-benzo [d] imidazol-3-ium bromide), 1- (carboxymethyl) pyridine-1-ium bromide (1- (carboxymethyl) pyridin-1-ium bromide), 4-carboxy-1- Methylpyridine-1-ium chloride (4-carboxy-1-methylpyridin-1-ium chloride), 3- (carboxymete 3- (carboxymethyl) -1-mesityl-1H-imidazol-3-ium chloride), 2-carboxy-N, N, N-trimethylethane At least one of -1-amnidium bromide (2-carboxy-N, N, N-trimethylethan-1-aminium bromide) and (3-carboxypropyl) triphenylphosphonium bromide It may include. When the compound of the above example is used as an onium salt compound containing a carboxylic acid group, the effect of preventing fouling while enhancing the reaction activity and increasing the apparent density of the polyketone compound prepared without adding a separate seed is further improved. Can be.

The onium salt compound including the carboxylic acid group may be included in a molar concentration of 0.1 × 10 ^-3 M to 1.0 × 10 ^-3 M. In this case, the polymerization stability and the activation degree in the polyketone production method is further improved, it is possible to produce a polyketone compound with excellent yield.

(Palladium-based catalyst)

The palladium-based catalyst used in the present invention is not particularly limited as long as it is a general palladium-based catalyst that can be used for polyketone polymerization.

The palladium-based catalyst is used that is not in a form supported on a carrier or the like. In addition, the above-mentioned sulfonic acid group is not used in the form of being previously supported on the surface-modified carrier, and is added during polymerization in separate states. In this case, fouling can be more effectively reduced while reducing the loss of activity of the palladium-based catalyst.

As the palladium-based catalyst, a Pd catalyst used for polyketone polymerization may be used.

The palladium-based catalyst may be represented by any one of the following Chemical Formulas 3 to 5.

[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 3 to 5, R ¹ to R ⁴ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and Y ¹ and Y ² are Each independently is a halogen anion or an oxyacetate anion, and Y ³ to Y ⁵ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an organosilicon group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or 6 to 6 carbon atoms; It is a 20 aromatic hydrocarbon group, Y <^6> is a C1-C10 alkylene group, a C3-C10 cycloalkylene group, or a C6-C20 divalent aromatic hydrocarbon group.

Specifically, the Y ³ to Y ⁵ And Each Y ⁶ may be substituted or unsubstituted, may or may not include one or more heteroatoms, and may be a monocyclic or polycyclic structure in the case of a ring structure.

The palladium-based catalyst may be used dispersed in a polymerization solvent (for example, an alcohol solvent). For example, after adding a palladium-based catalyst dispersed in a polymerization solvent to the reactor, the olefin gas and carbon monoxide gas are added to the mixture while stirring at room temperature and saturated, and the reactor is heated to copolymerize olefin and carbon monoxide.

In the polymerization reaction of the olefin and carbon monoxide, the palladium-based catalyst represented by any one of Formulas 3 to 5 may improve the copolymerization activity of the olefin and carbon monoxide, it is possible to prepare a polyketone compound.

The palladium-based catalyst is not particularly limited, but for example, 1,3-Bis (di-o-methoxyphenylphosphino) propane] Pd (OAc) ₂ catalyst, Pd (di-o-methoxyphenylphosphino) (diphenylphosphino) propane) (OAc) _It may be at least one selected from the group consisting of ₂ catalyst and Pd (1,3-bis (diphenylphosphino) propane) (OAc) ₂ catalyst. In this case, not only the copolymerization reactivity and activity of the olefin and carbon monoxide are more excellent, but also the effect of further preventing fouling phenomenon by interacting with the onium salt compound including the carboxylic acid group described above. In addition, in this case, not only the activity is excellent, but also the fouling phenomenon can be further prevented and a uniformly polymerized polyketone can be formed.

In particular, in the case of using the catalyst of the above example, the effect of controlling the morphology of the polyketone polymer synthesized around the catalyst by self aggregation of salt and palladium catalyst can be further improved. .

Specifically, the solvent of the catalyst system is an alcohol solvent, more specifically an alcohol compound having 1 to 20 carbon atoms, for example, methanol may be used. In this case, the polyketone production method may have higher reactivity and activation, and a lower boiling point, which may be advantageous in the aftertreatment process.

Polyketone  Catalyst Compositions for Compound Preparation

Another embodiment of the present invention relates to a palladium mixed catalyst system for producing a polyketone compound including the above-described catalyst composition for producing a polyketone compound and using olefin and carbon monoxide as reactants. In this case, specific contents of the catalyst composition are as described above.

Polyketone  Manufacturing method

Another embodiment of the present invention relates to a polyketone production method comprising the step of dispersing a catalyst composition for preparing a polyketone compound in a solvent and adding olefin and carbon monoxide to the dispersed catalyst composition.

In one embodiment, a polyketone production method includes a catalyst in which a surface-modified carrier is mixed with a palladium-based catalyst as a hetiro material, for example, a catalyst in which a palladium-based catalyst is supported on a carrier surface-modified with a sulfonic acid group. Has a distinct state, through which the shape and size of the final polyketone is uniformly adjusted when applied to the polyketone polymerization process, thereby improving the apparent density of the polyketone and preventing fouling during the process. The effect of improving the stability and activity of the polymerization reaction can be realized.

In another embodiment, a polyketone production method includes a salt of an onium salt compound containing a carboxylic acid group and a palladium catalyst in interaction to generate a heterogeneous seed having a fine size in a reaction solution, wherein the aggregate formed has a size of about 100 It is possible to control the particle size and shape of polyketone polymers formed very small in and around nm and to increase the apparent density very much. The polyketone production method of the present invention implements a high apparent density that is difficult to obtain by the conventional method of injecting a heterogeneous seed, and improves activity and prevents fouling by using only an additive while omitting seed addition. Can be.

As described above, when the polyketone is polymerized using the catalyst composition of the present invention, fouling can be prevented, and the particle shape of the resulting polyketone can be controlled by the shape of the modified carrier. In this case, polymer particles having a high apparent density may be generated to improve productivity.

Specific poly ketone is an onium salt compound having 5 to 40 carbon atoms containing a carrier or a carboxylic acid surface-modified sulfonic acid group used in the production method; And palladium-based catalyst; the details are as described above.

In the polymerization reaction, the solvent may be an alcohol compound having 1 to 20 carbon atoms.

In the polymerization reaction, the palladium-based catalyst may be included at a molar concentration of 0.1 × 10 ⁻³ M to 1.0 × 10 ⁻³ M. In this case, the polymerization stability and the activation degree in the polyketone production method is further improved, it is possible to produce a polyketone compound with excellent yield.

The onium salt compound including a carrier or a carboxylic acid group surface-modified by the sulfonic acid group in the polymerization reaction may be included in a molar concentration of 0.1 × 10 ^-3 M to 1.0 × 10 ^-3 M. In this case, the polymerization stability and the activation degree in the polyketone production method is further improved, it is possible to produce a polyketone compound with excellent yield.

In one embodiment, when the catalyst composition for preparing a polyketone compound includes a carrier modified with a sulfonic acid group, the method for producing a polyketone compound may further include preparing a carrier modified with a sulfonic acid group by adding sulfuric acid or chlorosulfuric acid to the carrier. It may include. At this time, specific details of the method for producing a surface-modified carrier with the sulfonic acid group are as described above.

As said olefin, for example, ethylene, propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, cyclopentene, norbornene, dicyclopenta Dienes, cyclooctene, cyclododecene, styrene, alphaketylstyrene, alkyl esters of (meth) acrylic acid and (meth) acrylic acid, and the like can be used. The said olefin can be used individually or in combination of 2 or more types.

More specifically, ethylene, propylene, hexene and decene may be used alone, or a mixture thereof may be used. In this case, the interaction with the catalyst is excellent, and the activity and yield of the polyketone polymer can be further increased.

In one embodiment, when using a mixture of 1 to 4 parts by weight of propylene based on 100 parts by weight of ethylene, it is possible to lower the melting temperature of the polyketone to be produced and to achieve excellent heat distortion temperature.

Specifically, the mole ratio of the olefin and the carbon monoxide may be 95: 5 to 5:95, more specifically 5: 1 to 1: 5 may be used in a molar ratio. In this case, the polyketone production method can further improve the reaction activity.

Specifically, the olefin and the carbon monoxide may be included in a ratio of 10 to 20 bar: 30 to 40 bar. In this case, the polyketone production method can further improve the reaction activity.

Specifically, the equivalent ratio of the onium salt compound including the carrier or the carboxylic acid group, the surface-modified sulfonic acid group; and the palladium-based catalyst may be 1: 0.1 to 1:10. In this case, the polyketone production method can further improve reaction activity and yield.

In one embodiment, the equivalent ratio of the carrier and the palladium-based catalyst surface-modified with the palladium-based catalyst and sulfonic acid group may be 1: 0.1 to 1: 2. More specifically, the equivalent ratio may be 1: 0.1 to 1: 1.2. It is possible to obtain higher catalyst activity and apparent density of a high polyketone polymer without fouling during polyketone polymerization using the catalyst composition in the above range.

In another embodiment, the equivalent ratio of the onium salt compound including the palladium-based catalyst and the carboxylic acid group may be 1: 0.1 to 1:10. In this case, the polyketone production method can further improve reaction activity and yield.

Specifically, the reaction temperature may be maintained in the range of 50 ° C to 150 ° C, more specifically 70 ° C to 130 ° C. In this case, the polyketone production method can further improve the reaction activity.

Specifically, the carbon monoxide and some olefins are gases at this temperature so that the polymerization reaction can be carried out in a pressure reactor. In this case, the polyketone manufacturing method can further improve reactivity and activation.

Specifically, the internal pressure of the reactor may be 200 atm or less, and more specifically 100 atm or less. In this case, the polyketone manufacturing method can further improve reactivity and activation.

Specifically, in the polyketone manufacturing method, the palladium mixed catalyst system for producing polyketone described above may exist in a dispersed state in a solvent to catalyze a polymerization reaction.

Specifically, the solvent is an alcohol solvent, more specifically an alcohol compound having 1 to 20 carbon atoms, for example, methanol can be used. In this case, the polyketone production method may have higher reactivity and activation, and a lower boiling point, which may be advantageous in the aftertreatment process.

In one embodiment, the carrier whose surface has been modified with the sulfonic acid group described above may be present in the form of a slurry without being dissolved in an organic solvent.

In another embodiment, the polyketone production method using the onium salt compound containing the carboxylic acid group described above may be a seed non-injection method.

Polyketone  polymer

Yet another embodiment of the present invention relates to a polyketone polymer formed by the aforementioned polyketone production method.

In one embodiment, the polyketone polymer formed by the above-described polyketone manufacturing method is that the carrier surface-modified by the sulfonic acid group is prepared by working with a palladium-based catalyst as a hetero material, the apparent density may be improved.

In another embodiment, the polyketone polymer formed by the aforementioned polyketone production method is shaped by a fine size heterogeneous seed formed by agglomeration of a salt of an onium salt compound containing the carboxylic acid group and a palladium catalyst together in an interaction. Can be controlled. In this case, the polyketone polymer formed with a very small aggregate size of about 100 nm may have a very high apparent density of 0.1 g / ml to 0.5 g / ml, for example, 0.27 g / ml to 0.47 g / ml. have.

Example

Hereinafter, the configuration and operation of the present invention through the embodiments of the present invention will be described in more detail. However, this is presented as a preferred example of the present invention and in no sense can be construed as limiting the present invention.

Production Example  One: Sulfonic acid group Surface modified Carrier  Produce

(Preparation of carrier)

To a 1 L beaker, 500 mL of methanol, 90 mL of H ₂ O, 32 mL of ammonium hydroxide solution, 1.2 g of hexadecyltrimethyl ammonium bromide (CTAB) were added, followed by stirring at 300 RPM for 30 minutes. It was. Tetraethyl orthosilicate (TEOS) was added while stirring at 300 RPM. The reaction was carried out at Room Temperature for 24hr while stirring at 300 RPM. Silica synthesized with Centrifuge was separated, washed with methanol and dried in an oven. The dried silica was then calcined at 550 ° C. for 5 h. The prepared silica was grinded finely with a mortar and then heated at 850 ° C. for 12 hours in an Ar furnace to prepare a carrier.

Benzyl magnesium chloride (benzyl magnesium chloride) was added to the silica carrier prepared above, and reacted with stirring at room temperature in a nitrogen atmosphere.

(Sulfonation)

Sulfuric acid was added to the benzyl group-attached silica carrier prepared as described above, and stirred overnight at room temperature to prepare a carrier (1.8 μm SiO ₂ -SO ₃ H) surface-modified with a sulfonic acid group. The surface of the prepared sulfonic acid group modified carrier was confirmed by SEM photographs, and the results are shown in FIG. 1.

Production Example  2: Sulfonic acid group Surface modified Carrier  Produce

(Preparation of carrier)

Zinc nitrate hexahydrate (1 eq, 0.1 mol, 297.49 g / mol, 29.75 g) was dissolved in 500 mL methanol to prepare a zinc nitrate solution, CTAB (Hexadecyltrimethyl ammonium bromide 99 +%, 0.25 eq, 0.025 mol, 364.45 g / mol, 9.1 g) was dissolved in 125 mL methanol to prepare a solution (CTAB Solution). In addition, 2-methyl imidazole (4 eq, 0.4 mol, 82.10 g / mol, 32.84 g) was dissolved in 500 mL methanol to prepare a solution (2-methylimidazole Solution).

100 mL of zinc nitrate solution prepared above was added to 250 mL RB (5 pieces), and 20 mL of CTAB Solution and 100 mL of 2-methylimidazole Solution were added sequentially, followed by stirring with 1100 RPM, followed by further 5 minutes of stirring. Then, the stirring was stopped and left for 18hr (RT) in a place where there was no vibration, and then the supernatant was discarded, and the prepared ZIF-8 was separated by centrifuge. The separated ZIF-8 carrier was washed twice with methanol, dried with a vacuum pump, and used as a template.

Flame-dry the 100 mL Schlenk flask and add Argon gas to the flask.Pd (PPh ₃ ) ₂ Cl ₂ (10 mol%, 0.024 mmol, 701.90 g / mol, 0.0168 g), CuI (10 mol%, 0.024 mmol, 190.45 g / mol, 0.0046 g), and 0.4 g of the previously prepared carrier ZIF-8 were added sequentially. To this, additional TEA (Triethylamine 60 mL) was added and dispersed in Sonicator for 1.5 h to prepare a dispersion. Tetra- (4-ethynylphenyl) -methane (1 eq, 0.24 mmol, 416.51 g / mol, 0.1 g) and 1,4-Diiodobenzene (2 eq, 0.48 mmol, 329.90 g / mol, 0.1584 g) were added to the dispersion. And dispersed again in the Sonicator for 5 minutes. Thereafter, the reaction was performed at 100 ° C. for 24 h, cooled to room temperature, and a carrier (ZIF-8 @ MON) in the form of a hollow structure including the previously prepared carrier ZIF-8 synthesized as a centrifuge as a template was separated. The synthesized carrier was washed twice in the order of acetone, dichloromethane, methanol, acetone, and dried with a vacuum pump.

In addition, the carrier (ZIF-8 @ MON, 0.16 g) prepared above and 15 mL of methanol were dispersed in a Falcon tube, 20 mL of acetic acid was added thereto, followed by etching for 1 h. Etching further promoted the formation of a microporous organic network in the carrier. Then, the carrier (HMON) etched with Centrifuge was separated, washed 10 times with methanol (MeOH), twice with acetone (Acetone), dried with a vacuum pump and used for sulfonation.

(Sulfonation)

Argon gas was added after flame drying the 100 mL Schlenk flask. In the flask, a carrier (HMON 0.04 g) and 20 mL of dichloromethane, which is a hollow structure containing a microporous organic network, were added and dispersed well. After dispersion, the temperature was lowered to 0 ° C., and then 0.6 mL of ClSO ₃ H was added very slowly, the temperature was raised to RT, and reacted for 1.5 h under Ar. The temperature is lowered to 0 ° C., and methanol is added to quench remaining ClSO ₃ H. The surface-modified carrier with sulfonic acid was separated by a centrifuge, washed with a solution of methanol and H ₂ O at 2: 1, and then washed twice with Methanol, and dried twice with Methanol.

The surface-modified carriers prepared with sulfonic acid groups were identified by SEM (a, b) and TEM (c) of FIG. 3, and the results are shown in FIG. 3.

Production Example  3: Sulfonic acid group Surface modified Carrier  Produce

(Preparation of carrier)

200 mL of ethanol (Ethanol) was added to a 250 mL round bottomed flask, and 23 mL of distilled H ₂ O and 7 mL (28-30%) of Ammonium hydroxide solution were added thereto, followed by stirring at 300 RPM for 30 minutes. Thereafter, 18 mL of TEOS (Tetraethyl orthosilicate, 1eq 0.081 mol, 208.33 g / mol 0.933 g / mL) was added thereto, and the reaction was performed rapidly at room temperature for 18 h. Add 5 drops of acetic acid, add 100 mL hexane and 150 mL dichloromethane, shake, separate the aggrigation silica with centrifuge, wash 3 times with a solution of 1: 1 mixed with hexane and dichloromethane, and then 80 The silica carrier was prepared as a template by heating to dryness.

Flame-dry the 100 mL Schlenk flask and add Argon gas to the flask.Pd (PPh ₃ ) ₂ Cl ₂ (10 mol%, 0.024 mmol, 701.90 g / mol, 0.0168 g), CuI (10 mol%, 0.024 mmol, 190.45 g / mol, 0.0046 g), and 0.6 g of the carrier silica carrier prepared above were added in this order. To this, further added TEA (Triethylamine 60 mL) was dispersed well in the Sonicator for 1.5 h to prepare a dispersion. Tetra- (4-ethynylphenyl) -methane (1 eq, 0.24 mmol, 416.51 g / mol, 0.1 g) and 1,4-Diiodobenzene (2 eq, 0.48 mmol, 329.90 g / mol, 0.1584 g) were added to the dispersion. And dispersed again in the Sonicator for 5 minutes. Thereafter, after reacting at 100 ° C. for 24 h, the mixture was cooled to room temperature, and the carrier (SiO ₂ @MON) containing the previously prepared silica carrier synthesized with Centrifuge as a template and containing a microporous organic network layer was separated. It was. The synthesized carrier was washed twice in the order of acetone, dichloromethane, methanol, acetone, and dried with a vacuum pump.

(Sulfonation)

Argon gas was added after flame drying the 100 mL Schlenk flask. In the flask, a silica carrier was included as a template, and a carrier including a microporous organic network layer (SiO ₂ @MON 0.72 g) and 60 mL of dichloromethane were added and dispersed well. After dispersion, the temperature was lowered to 0 ° C., and then 1.8 mL of ClSO ₃ H was added very slowly, the temperature was raised to RT, and the reaction was continued for 1.5 h under Ar. After lowering the temperature to 0 ℃, Methanol was added to quench the remaining ClSO ₃ H. The surface-modified carrier with sulfonic acid was separated by centrifuge, washed with methanol (Methanol) and H ₂ O in a 2: 1 solution at pH 7, and washed twice with Methanol and dried with vacuum pump.

Production Example  4: Sulfonic acid group Surface modified Carrier  Produce

(Preparation of reactants for carrier preparation)

Styrene Purification: Styrene stabilizer (4-tert-butylcatechol) removal

Add 30 mL of dichloromethane to 200 mL styrene. 50mL of 1M Sodium hydroxide solution is added to the mixed solution and extracted three times. After dehydration with magnesium sulfate, dichloromethane is removed using a vacuum pump. Refrigerated under argon after blocking light.

-Divinylbenzene purification: removal of stabilizer (4-tert-butylcatechol) of divinylbenzene

Add 10 mL of dichloromethane to 80 mL styrene. 50mL of 1M Sodium hydroxide solution is added to this mixed solution and extracted three times. After dehydration with magnesium sulfate, dichloromethane is removed using a vacuum pump. Block the light and store frozen under Ar.

(Preparation of carrier)

Flame dry the 100 mL one neck Schlenk flask and add Argon gas. After distilled water is added, styrene (Styrene) and divinylbenzene (purified previously) are added and heated to 65 ° C. Blow the argon gas to remove the gas from the solution and stir for at least 15 minutes until the emulsion is formed. Potassium persulfate was dissolved in distilled water in the mixed solution and reacted at 65 ° C. for 20 h. After the reaction, put it in the freezer for 2h and raise the temperature to room temperature. After dilution with about 80mL Ethanol, polystyrene (Polystyrene powder) prepared by Centrifuge was separated, washed 5 times with ethanol and dried by vacuum pump.

(Sulfonation)

Flame dry the 50 mL one neck Schlenk flask and add Argon gas. Polystyrene powder and sulfuric acid are added and sonication is performed for 30 minutes. After stirring at 40 ° C. for 18 hours or more, the mixture is cooled to room temperature. Dilute with methanol and centrifuge to settle. Wash with a solution of Methanol and H2O 2: 1 when the pH is 7 After washing twice more with methanol and dried with a vacuum pump.

Production Example  5: Surface is not modified  Not Carrier  Produce

A carrier was prepared in the same manner as in Preparation Example 2, except that the sulfonation step was omitted.

Table 1 shows the physical properties of the carriers prepared in Preparation Examples 1 to 5.

Carrier Type Particle size Surface area (m ² / g) Pore volume (mL / g) Pore radius (nm) Sulfonation SO ₃ H amount (mmol-H + / g) Preparation Example 1 1.8 μm 857.06 0.3964 1.85 ○ 0.1795 Preparation Example 2 450 nm 622.91 0.4503 2.8918 ○ 2.1543 Preparation Example 3 450 nm 64.294 0.0815 5.0722 ○ 0.4519 Preparation Example 4 800 nm 5.62 0.0346 24.606 ○ 0.862 Preparation Example 5 450 nm 622.91 0.4503 2.8918 X -

Example  One

To 1.0 mg of Pd (1,3-bis (di (2-methoxyphenyl) phosphinopropane) (OAc) _2, 2.7 mg of surface-modified carrier (1.8 μm SiO ₂ -SO ₃ H) prepared in Preparation Example 1 was added to methanol (10 mL) and mixed at room temperature to prepare a catalyst composition.

After immersing the catalyst composition in a high pressure reactor (˜50 mL size), the reactor was assembled and saturated by adding 25 bar of ethylene gas and 35 bar of CO while stirring at room temperature. The temperature of the reactor was raised to 90 ° C. to carry out polymerization for about 15 hours. After the reaction, 4.8 g of polyketone powder was obtained. (Activity 33.84 Kg / g-Pd; 1.29 kg / g-catalyst, apparent density 0.297 g / mL)

After the polyketone was prepared by the method of Example 1, the sulfonated carrier prepared in Preparation Example 1 used for the reaction was collected and the SEM measured photo was shown in FIG. 2.

A photograph of the prepared polyketone is shown in FIG. 5, and it was visually confirmed that fouling did not occur.

Example 2

To 1.5 mg of Pd (1,3-bis (di (2-methoxyphenyl) phosphinopropane) (OAc) ₂ was added 4.0 mg of surface modified carrier (1.8 μm SiO ₂ -SO ₃ H) prepared in Preparation Example 1 in methanol (10 mL). ), And the mixture was mixed at room temperature to prepare a catalyst composition, which was carried out in the same manner as in Example 1. After the reaction, 4.95 g of polyketone powder was obtained (activity 23.26 kg / g-Pd; 0.90 kg). / g-catalyst, apparent density 0.309 g / mL)

Example 3

0.6 mg of Pd (1,3-bis (di (2-methoxyphenyl) phosphinopropane) (OAc) ₂ was added to methanol (20 mL) in 0.8 mg of the surface-modified carrier prepared in Preparation Example 2, and the same as in Example 1 above. 5.6 g of polyketone powder were obtained after the reaction (activity: 61.23 Kg / g-Pd; 4.08 kg / g-catalyst, apparent density 0.374 g / mL).

Before preparing the polyketone by the method of Example 3, the surface of the carrier modified with the sulfonic acid group prepared in Preparation Example 2 was collected and the SEM measurement is shown in Figure 4 (a).

After preparing the polyketone by the method of Example 3, the surface-modified carrier obtained by the sulfonic acid group prepared in Preparation Example 2 used in the reaction was collected and the SEM measurement is shown in Figure 4 (b).

Referring to FIG. 4, the carrier surface-modified with the sulfonic acid group of Preparation Example 2 before the reaction had a diameter of 521 nm and a thickness of 20 nm, and changed to 625 nm in diameter and 120 nm in thickness after the reaction.

Example 4

1.0 mg of the surface-modified carrier prepared in Preparation Example 3 was added to 1.0 mg of Pd (1,3-bis (di (2-methoxyphenyl) phosphinopropane) (OAc) ₂ in methanol (10 mL). After the reaction, 3.7 g of polyketone powder was obtained (activity 26.53 kg / g-Pd; 1.86 kg / g-catalyst, apparent density 0.310 g / mL).

A photograph of the prepared polyketone is shown in FIG. 7, and it was visually confirmed that fouling did not occur.

Example 5

To 1.5 mg of Pd (1,3-bis (di (2-methoxyphenyl) phosphinopropane) (OAc) _2, 1.0 mg of the surface-modified carrier prepared in Preparation Example 4 was added to methanol (10 mL) at room temperature. The catalyst composition was carried out in the same manner as in Example 1, except that the catalyst composition was mixed to obtain 2.5 g of polyketone powder after the reaction (activity: 11.94 kg / g-Pd; 1.02 kg / g-catalyst, apparent) Density 0.318 g / mL)

Example 6

The palladium catalyst was used as above except that 0.8 mg of Pd (1,3-bis (diphenylphosphino) propane) (OAc) _{2 was used} instead of Pd (1,3-bis (di (2-methoxyphenyl) phosphinopropane) (OAc) ₂ . The same procedure was followed as in Example 1. After the reaction, 0.265 g of polyketone powder was obtained (activity 1.89 Kg / g-Pd; 0.135 kg / g-catalyst; apparent density 0.389 g / mL).

Comparative Example 1

The preparation of the catalyst composition was carried out in the same manner as in Example 2, except that the carrier whose surface was modified was not added. (Catalytic activity 0.478 kg / g-Pd)

Comparative Example 2

The reaction was carried out in the same manner as in Example 2, except that paratoluene sulfonic acid was added instead of the carrier having the surface-modified reaction. After the reaction, 1.33 g of polyketone powder was obtained. (Activity 6.27 kg / g-Pd; 0.814 kg / g-catalyst)

Photographs of the prepared polyketone are shown in FIG. 8, and it was visually confirmed that fouling occurred.

Comparative Example 3

Except that 0.4 mg of the carrier of Preparation Example 5 containing no sulfonic acid group was added to 1.5 mg of Pd (dmppp) (OAc) ₂ into methanol (10 mL) and mixed at room temperature to prepare a catalyst composition. It carried out similarly to Example 2. (Catalytic activity 0.771 kg / g-Pd)

Comparative Example 4

The preparation of the catalyst composition was carried out in the same manner as in Comparative Example 2, except that Amberlyst 15 was added as a carrier modified with a sulfonic acid group. 0.64 g of polyketone powder was obtained after the reaction. (Activity 3.01 kg / g-Pd; 0.388 kg / g-catalyst)

A photograph of the prepared polyketone is shown in FIG. 9, and it was visually confirmed that fouling occurred.

Catalytic Activity 1 (kg / g-Pd) Catalytic activity 2 (kg / g-catalyst) Apparent density (g / mL) Fouling occurrence drawing Example 1 33.84 1.29 0.297 radish 5 Example 2 23.26 0.9 0.309 radish - Example 3 61.23 4.08 0.374 radish 6 Example 4 26.5 1.86 0.310 radish 7 Example 5 11.94 1.02 0.318 radish - Example 6 1.89 0.135 0.389 radish - Comparative Example 1 0.427 Not measurable U - Comparative Example 2 6.27 0.81 Not measurable U 8 Comparative Example 3 0.771 Not measurable U - Comparative Example 4 3.00 0.388 Not measurable U 9

Example 7

After dispersing [1,3-Bis (di-o-methoxyphenylphosphino) propane] Pd (OAc) ₂ catalyst (2 μmol) in methanol (MeOH, 10 ml) in a high pressure reactor (50 mL size), the reactor was assembled, While stirring at room temperature, 25 bar of ethylene gas and 35 bar of carbon monoxide (CO) were added and saturated. Thereafter, the additives shown in Table 3 were added to the reactor, and the reactor temperature was raised to 90 ° C., and polymerization reaction was performed at 62 bar for about 15 hours. After the completion of the polymerization reaction, the reaction mass was cooled to room temperature, filtered, and dried in an oven at 65 ° C. for 1 hour to obtain a polyketone polymer powder.

Examples 8-16 and Comparative Examples 5-12

The polymerization reaction was carried out in the same manner as in Example 7, except that the composition of the component added to the reaction was changed as shown in Table 3 below.

Catalyst type Catalyst content (μmol / weight) additive Additive content (eq./weight) Example 7 Catalyst A 2.0 / 1.5mg Additive 1A 1 / 0.3 mg Example 8 Catalyst A 2.0 / 1.5mg Additive 1A 0.75 / 0.26 mg Example 9 Catalyst A 2.0 / 1.5mg Additive 1A 0.5 / 0.15 mg Example 10 Catalyst A 2.0 / 1.5mg Additive 1B 0.75 / 0.5 mg Example 11 Catalyst A 2.0 / 1.5mg Additive 1C 0.75 / 0.3 mg Example 12 Catalyst A 2.0 / 1.5mg Additive 1D 0.75 / 0.6 mg Example 13 Catalyst A 2.0 / 1.5mg Additive 1E 0.75 / 0.3 mg Example 14 Catalyst A 2.0 / 1.5mg Additive 1F 0.75 / 0.4 mg Example 15 Catalyst A 2.0 / 1.5mg Additive 1G 0.75 / 0.3 mg Example 16 Catalyst A 2.0 / 1.5mg Additive 1H 0.75 / 0.3 mg Example 17 Catalyst A 2.0 / 1.5mg Additive 1A 0.75 / 0.23 mg Example 18 Catalyst A 2.0 / 1.5mg Additive 1I 0.75 / 0.4 mg Example 19 Catalyst A 2.0 / 1.5mg Additive 1J 0.75 / 0.3 mg Example 20 Catalyst A 2.0 / 1.5mg Additive 1K 0.75 / 0.65 mg Example 21 Catalyst B 2.0 / 1.4mg Additive 1B 0.75 / 0.5 mg Example 22 Catalyst C 2.0 / 1.3mg Additive 1B 0.75 / 0.5 mg Comparative Example 5 Catalyst A 2.0 / 1.5mg none 0 Comparative Example 6 Catalyst A 2.0 / 1.5mg Additive 2 4.0 (μmol) Comparative Example 7 Catalyst A 2.0 / 1.5mg Additive 2 2.0 (μmol) Comparative Example 8 Catalyst A 2.0 / 1.5mg Additive 3 1.5 (μmol) Comparative Example 9 Catalyst A 2.0 / 1.5mg Additive 4 1.5 (μmol) Comparative Example 10 Catalyst A 2.0 / 1.5mg Additive 5 1.5 (μmol) Comparative Example 11 Catalyst A 2.0 / 1.5mg Additive 6 1.5 (μmol) Comparative Example 12 Catalyst A 2.0 / 1.5mg Additives 7 1.5 (μmol)

The kinds of palladium catalysts used in Examples 7 to 22 and Comparative Examples 5 to 12 are as follows.

[Catalyst A]

: 1,3-Bis (di-o-methoxyphenylphosphino) propane] Pd (OAc) ₂

[Catalyst B]

: Pd (di-o-methoxyphenylphosphino) (diphenylphosphino) propane) (OAc) ₂

[Catalyst C]

: Pd (1,3-bis (diphenylphosphino) propane) (OAc) ₂

[Catalyst D]

: 1,3-Bis (di-o-methoxyphenylphosphino) propane] Pd (Cl) ₂

The types of additives used in Examples 7 to 22 and Comparative Examples 5 to 12 are as follows.

[Additive 1A]

: Glycine betaine hydrochloride

[Additive 1B]

3- (carboxymethyl) -1-mesityl-1H-imidazole-3-ium chloride (3- (carboxymethyl) -1-mesityl-1H-imidazol-3-ium chloride)

[Additive 1C]

Trigonelline hydrochloride

[Additive 1D]

: 3- (carboxymethyl) -1- (2,6-diisopropylphenyl) -1H-imidazole-3-ium bromide (3- (carboxymethyl) -1- (2,6-diisopropylphenyl) -1H-imidazol -3-ium bromide)

[Additive 1E]

3- (carboxymethyl) -1-methyl-1H-imidazole-3-ium bromide (3- (carboxymethyl) -1-methyl-1H-imidazol-3-ium bromide)

[Additive 1F]

3- (carboxymethyl) -1-methyl-1H-benzo [d] imidazol-3-ium bromide (3- (carboxymethyl) -1-methyl-1H-benzo [d] imidazol-3-ium bromide)

[Additive 1G]

: 1- (carboxymethyl) pyridine-1-ium bromide (1- (carboxymethyl) pyridin-1-ium bromide)

[Additive 1H]

4-carboxy-1-methylpyridine-1-ium chloride (4-carboxy-1-methylpyridin-1-ium chloride)

[Additive 1I]

3- (carboxymethyl) -1-mesityl-1H-imidazole-3-ium chloride (3- (carboxymethyl) -1-mesityl-1H-imidazol-3-ium chloride)

[Additive 1J]

2-carboxy-N, N, N-trimethylethane-1-aminium bromide (2-carboxy-N, N, N-trimethylethan-1-aminium bromide)

[Additive 1K]

((3-carboxypropyl) triphenylphosphonium bromide)

[Additive 2]

[Additive 3]

[Additive 4]

[Additive 5]

[Additive 6]

[Additive 7]

The activation degrees of the polymerization reactions performed in Examples 7 to 22 and Comparative Examples 5 to 12 are shown in Table 4 below.

Fouling Occurs Activation (Kg / g-Pd) Yield (g) Density (g / ml) Example 7 radish 17 3.5 0.27 Example 8 radish 22 4.8 0.32 Example 9 radish 15 3.2 0.27 Example 10 radish 19 4.1 0.47 Example 11 radish 20 4.2 0.31 Example 12 radish 16.2350 3.4548 0.2658 Example 13 radish 18.8901 4.0198 0.3654 Example 14 radish 13.3524 2.8414 0.406 Example 15 radish 6.6871 1.4230 0.2453 Example 16 radish 19.7486 4.2033 0.3110 Example 17 radish 22.3595 4.7581 0.321 Example 18 radish 16.2354 3.4549 0.2658 Example 19 radish 1.4187 0.3019 - Example 20 radish 1.1118 0.2366 - Example 21 radish 4.6537 0.9903 0.3301 Example 22 radish 3.2730 0.6965 0.2322 Comparative Example 5 U 0.48 0.1 - Comparative Example 6 U 24 5.0 - Comparative Example 7 U 21 4.4 - Comparative Example 8 U 0.72 0.15 - Comparative Example 9 U 0.29 0.06 - Comparative Example 10 U 1.3 0.27 - Comparative Example 11 U 0.29 0.06 - Comparative Example 12 U 0.38 0.08 -

As can be seen through Table 3 and Table 4, Examples 7 to 22 according to the polyketone production method of the present invention described above can prevent fouling by using an onium salt compound containing a carboxylic acid group as an additive , It was confirmed that the stability and activity in the polymerization reaction is excellent.

On the other hand, Comparative Example 5, which does not contain any additives, showed very low activity, and Comparative Examples 6 and 7 using strong acid para-toluenes (p-toluenesulfonic acid, TsOH) as additives confirmed that fouling occurred. . In addition, Comparative Examples 8 to 12 using No. 3 to No. 7 having a structure completely different from the present invention by not containing any carboxylic acid group or containing no onium salt compound had very low activity and sufficiently formed polyketone polymers. It was confirmed that fouling was not only difficult but also occurred.

Simple modifications or changes of the present invention can be easily made by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (27)

An onium salt compound having 5 to 40 carbon atoms including a carrier or a carboxylic acid surface-modified sulfonic acid group; And Palladium-based catalysts; Catalyst composition for producing a polyketone compound comprising a. The method of claim 1, The catalyst composition surface-modified by the sulfonic acid group is a catalyst composition for producing a polyketone compound comprising a structure in which a functional group represented by any one of the following formula 1-1 to 1-3 bonded to the carrier surface: [Formula 1-1] * -SO ₃ H In Chemical Formula 1-1, * means a portion bonded to the surface of the carrier; [Formula 1-2]

In Formula 1-2, R ²¹ to R ²⁶ are each independently hydrogen or alkyl of C1 to C20; * Means the moiety bonded to the surface of the carrier; [Formula 1-3]

In Formula 1-3, R ³¹ to R ³⁴ are each independently hydrogen or alkyl of C1 to C20; * Denotes the part that is bonded to the carrier surface. it means. The method of claim 2, The carrier may be silica, zeolite, graphite, carbon black, graphene, carbon nanotube, activated carbon, polystyrene, microporous organic network, metal organic structure (MOF), zeolite-like structure (ZIF), organic skeleton A catalyst composition for producing a polyketone compound comprising at least one of a structure (COF) and a biopolymer including cellulose. The method of claim 3, The catalyst composition surface-modified sulfonic acid group is a catalyst composition for producing a polyketone compound which is a hollow structure comprising a microporous organic network (microporous organic network) having a repeating unit represented by the formula 1-4: [Formula 1-4]

In Formula 1-4, A is a linking portion of an atom. The method of claim 3, The sulfonic acid group-modified carrier includes a silica carrier and a catalyst for producing a polyketone compound including a microporous organic network polymer layer having a repeating unit represented by the following Formula 1-5 formed on the surface of the silica carrier. Composition: [Formula 1-5]

In Formula 1-5, each A ′ independently represents a linking site between a linking unit or a repeating unit of an atom bonded to a carrier, and at least one of A ′ is a linking site of an atom bonded to a carrier, and at least At least one is the link between repeat units. The method of claim 3, A catalyst composition for preparing a polyketone compound, wherein the carrier having a surface-modified sulfonic acid group comprises a polystyrene compound having a repeating unit represented by Formula 1-6: [Formula 1-6]

In Chemical Formula 1-6, R ⁶ is a sulfonic acid group, a para-toluenesulfonic acid group, or a benzene sulfonic acid group, and n is 10 to 20,000. The method of claim 3, The surface-modified carrier of the sulfonic acid group is a silica carrier and a catalyst composition for producing a polyketone compound in which the functional group represented by any one of Formulas 1-2 to 1-3 is Si-C bonded. The method of claim 1, The catalyst composition for producing a polyketone compound in the form of a surface-modified carrier and the palladium-based catalyst dispersed in a solvent. The method of claim 8, The solvent is a catalyst composition for producing a polyketone compound is an alcohol compound having 1 to 20 carbon atoms. The method of claim 1, A catalyst composition for producing a polyketone compound, wherein the onium salt compound having 5 to 40 carbon atoms including the carboxylic acid group is represented by the following Formula 2. [Formula 2] [Z-COOH] ⁺ [X] ^- In Formula 2, Z is a hydrocarbon group having 1 to 20 carbon atoms containing nitrogen, phosphorus or sulfur; [X] ^- is an anion (anion) containing a halogen, oxygen, boron, phosphorous, sulfur, or a combination thereof. The method of claim 10, In Chemical Formula 2, Z is a catalyst composition for preparing a polyketone compound which is an aromatic heterocyclic group. The method of claim 10, In Chemical Formula 2, Z is a branched heteroalkyl catalyst composition for preparing a polyketone compound. The method of claim 10, The compound of Formula 2 is glycine betaine hydrochloride (glycine betaine hydrochloride), trigonelline hydrochloride (trigonelline hydrochloride), 3- (carboxymethyl) -1-mesityl-1H-imidazole-3-ium bromide (3- (carboxymethyl) -1-mesityl-1H-imidazol-3-ium bromide), 3- (carboxymethyl) -1- (2,6-diisopropylphenyl) -1H-imidazole-3-ium bromide (3- (carboxymethyl) -1- (2,6-diisopropylphenyl) -1H-imidazol-3-ium bromide), 3- (carboxymethyl) -1-methyl-1H-imidazole-3-ium bromide (3- (carboxymethyl) -1-methyl-1H-imidazol-3-ium bromide), 3- (carboxymethyl) -1-methyl-1H-benzo [d] imidazol-3-ium bromide (3- (carboxymethyl) -1-methyl- 1H-benzo [d] imidazol-3-ium bromide), 1- (carboxymethyl) pyridine-1-ium bromide (1- (carboxymethyl) pyridin-1-ium bromide), 4-carboxy-1-methylpyridine-1 4-carboxy-1-methylpyridin-1-ium chloride, 3- (carboxymethyl) -1-mesh -1H-imidazol-3-ium chloride (3- (carboxymethyl) -1-mesityl-1H-imidazol-3-ium chloride), 2-carboxy-N, N, N-trimethylethane-1-aminium bromide Polyketone containing one or more of (2-carboxy-N, N, N-trimethylethan-1-aminium bromide) and (3-carboxypropyl) triphenylphosphonium bromide Catalyst composition for preparing the compound. The method of claim 1, The palladium-based catalyst is a catalyst composition for producing a polyketone compound represented by any one of the following formulas (3) to (5). [Formula 3]

[Formula 4]

[Formula 5]

In Formulas 3 to 5, R ¹ to R ⁴ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and Y ¹ and Y ² are Each independently is a halogen anion or an oxyacetate anion, and Y ³ to Y ⁵ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an organosilicon group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or 6 to 6 carbon atoms; It is a 20 aromatic hydrocarbon group, Y <^6> is a C1-C10 alkylene group, a C3-C10 cycloalkylene group, or a C6-C20 divalent aromatic hydrocarbon group. The method of claim 1, The palladium-based catalysts include 1,3-Bis (di-o-methoxyphenylphosphino) propane] Pd (OAc) ₂ catalyst, Pd (di-o-methoxyphenylphosphino) (diphenylphosphino) propane) (OAc) ₂ catalyst and Pd (1,3 A catalyst composition for producing at least one polyketone compound selected from the group consisting of -bis (diphenylphosphino) propane) (OAc) ₂ catalyst. The method of claim 1, A catalyst composition for producing a polyketone compound having an equivalent ratio of the onium salt compound including the carrier or the carboxylic acid group surface-modified by the sulfonic acid group and the palladium-based catalyst is 1: 0.1 to 1:10. A palladium mixed catalyst system for producing a polyketone compound, comprising the catalyst composition for producing a polyketone compound according to claim 1 and using olefin and carbon monoxide as reactants. Dispersing the catalyst composition for producing a polyketone compound according to claim 1 in a solvent, Polyketone manufacturing method comprising the step of polymerizing by adding olefin and carbon monoxide to the dispersed catalyst composition. The method of claim 18, The solvent is a polyketone production method of an alcohol compound having 1 to 20 carbon atoms. The method of claim 18, Onium salt compound comprising a carrier or a carboxylic acid surface-modified sulfonic acid group is a polyketone production method is introduced at a molar concentration of 0.1 × 10 ^-3 M to 1.0 × 10 ^-3 M. The method of claim 18, The catalyst composition for producing a polyketone compound includes a carrier surface-modified with a sulfonic acid group, A carrier modified with a sulfonic acid group is a polyketone production method is prepared by adding sulfuric acid or chlorosulfuric acid to the carrier. The method of claim 18, The palladium-based catalyst is a polyketone production method that is included in a molar concentration of 0.1 × 10 ^-3 M to 1.0 × 10 ^-3 M. The method of claim 18, Wherein said olefin is ethylene, propylene, hexene, decene or mixtures thereof. The method of claim 18, Wherein the olefin and the carbon monoxide is 20 to 30 bar: 30 to 40 bar in the ratio of polyketone production method. The method of claim 18, The polymerization reaction is carried out at 50 ℃ to 150 ℃ polyketone production method. The method of claim 18, The polyketone production method is a seed non-injection method polyketone production method. A polyketone polymer formed by the polyketone production method according to claim 18 and having an apparent density of 0.1 to 0.5 g / ml.

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