CN109312145B

CN109312145B - Catalyst composition for preparing polyketone compound, palladium mixed catalyst system, method for preparing polyketone compound using the same, and polyketone polymer

Info

Publication number: CN109312145B
Application number: CN201780035036.5A
Authority: CN
Inventors: 张慧暎; 李泍烈; 林有娜; 孙性旭; 朴鲁镇; 姜信宁; 卢炯完; 郑然州
Original assignee: Ajou University Industry Academic Cooperation Foundation
Current assignee: Ajou University Industry Academic Cooperation Foundation
Priority date: 2016-08-19
Filing date: 2017-08-18
Publication date: 2021-03-16
Anticipated expiration: 2037-08-18
Also published as: WO2018034549A1; CN109312145A

Abstract

The present invention relates to a catalyst composition for preparing polyketone compounds, which is characterized by comprising: an onium salt compound having 5 to 40 carbon atoms, including a carrier or a carboxylic acid group whose surface is modified with a sulfonic acid group; and palladium-based catalysts. Thus, the present invention can provide a palladium mixed catalyst system that exhibits high activity in the production of polyketone and prevents fouling, and by utilizing the above-mentioned palladium mixed catalyst system can also provide a palladium mixed catalyst system capable of preventing fouling and omitting the addition of seeds, during polymerization A method for preparing a polyketone compound having good stability and activity during reaction and a polyketone polymer having a high apparent density prepared therefrom.

Description

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

Technical Field

The present invention relates to a palladium mixed catalyst system which can exhibit high activity and prevent fouling in the preparation of polyketone, a method for preparing polyketone compounds using the mixed catalyst system, and polyketone polymers prepared thereby.

Background

Polyketone is a polymer known as a carbon monoxide/olefin copolymer. Recently, polyketones are actively used as a raw material for high-strength fibers, engineering plastics, and the like, and thus the demand thereof is also increasing. The synthesis of such polyketones has good industrial applicability in converting carbon monoxide into useful substances and in being able to provide polymer compounds excellent in physical properties.

In existing polyketone production processes, the catalyst is dissolved in methanol and then fed into a reactor to polymerize carbon monoxide and ethylene under pressure into polyketone. In this conventional polyketone production method, polymerization is carried out in a homogeneous state dissolved in methanol, and as a result, amorphous slurry-type polyketone (a copolymer of carbon monoxide and ethylene) having no solubility in a solvent is formed.

However, the conventional polyketone in the form of an amorphous slurry cannot adjust its particle shape, and thus has problems of low apparent density and low productivity per unit volume of a reactor. Such amorphous slurry-type polyketone particles adhere to reactor surfaces, stirrers, transfer pipes, etc., thereby causing fouling problems in the mass production process.

Further, in the conventional polyketone production method, it is difficult to improve the activity to a level having industrial applicability without directly using an additive such as sulfonic acid (sulfonic acid), but when a strongly acidic additive is used, there is a problem that scaling is easily generated, and thus it is difficult to apply to a mass production process.

Therefore, there is an increasing need to develop a process for preparing polyketone which can adjust the particle shape, prevent the occurrence of the fouling phenomenon during the polymerization reaction, and improve the reactivity to an industrially useful level.

Disclosure of Invention

Problems to be solved by the invention

An object of the present invention is to provide a catalyst composition which can improve apparent density by uniformly controlling the shape and size of polyketone finally prepared, prevent a fouling phenomenon occurring in a process, and improve stability and activity of polymerization reaction.

It is another object of the present invention to provide a palladium mixed catalyst system which can exhibit high activity and prevent fouling in the preparation of polyketone by using an onium salt compound substituted with a carboxylic acid as an additive.

It is still another object of the present invention to provide a method for preparing polyketone compounds, which can prevent fouling and omit the addition of seeds, and has good stability and activity in polymerization reaction, by using the above catalyst composition and palladium mixed catalyst system, and polyketone polymers prepared thereby having high apparent density.

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

Means for solving the problems

One embodiment of the present invention relates to a catalyst composition for preparing polyketone compounds, characterized by comprising: onium salt compounds having 5 to 40 carbon atoms including a support surface modified with sulfonic acid groups or carboxylic acid groups; and a palladium-based catalyst.

Another embodiment of the present invention relates to a palladium mixed catalyst system for the preparation of polyketones, characterized in that it comprises the above catalyst composition for the preparation of polyketones, using olefins and carbon monoxide as reactants.

Still another embodiment of the present invention relates to a method for preparing polyketone, comprising: a step of dispersing a catalyst composition for preparing a polyketone compound in a solvent; and a step of adding an olefin and carbon monoxide to the dispersed catalyst composition to carry out polymerization.

Yet another embodiment of the present invention relates to a polyketone polymer characterized by having an apparent density of 0.1 to 0.5g/ml formed by a process according to the above polyketone preparation.

ADVANTAGEOUS EFFECTS OF INVENTION

The present invention can provide a catalyst composition capable of exhibiting high activity and preventing fouling in the preparation of polyketone and a palladium mixed catalyst system comprising the same, and can also provide a method for preparing polyketone compounds capable of preventing fouling, adjusting the shape and size of polyketone, omitting the addition of seeds, and having good stability and activity at the time of polymerization reaction, and polyketone polymers having high apparent density prepared therefrom, by using the above mixed catalyst system.

Drawings

Fig. 1 is an SEM photograph of the support surface-modified with sulfonic acid groups prepared in preparation example 1.

Fig. 2 is an SEM photograph of the support surface-modified with sulfonic acid groups of preparation example 1 recovered after the polymerization reaction of example 1 was performed.

Fig. 3 is an electron micrograph of the support surface-modified with sulfonic acid groups prepared in preparation example 2.

FIG. 4 is SEM photographs comparing (a) before and (b) after applying the support surface-modified with sulfonic acid groups prepared in preparation example 2 to polyketone preparation of example 3.

FIG. 5 is a photograph of polyketone prepared in example 1.

FIG. 6 is a photograph of polyketone prepared in example 3.

FIG. 7 is a photograph of polyketone prepared in example 4.

FIG. 8 is a photograph of polyketone prepared in comparative example 2.

FIG. 9 is a photograph of polyketone prepared in comparative example 4.

Fig. 10 shows a support 100 surface-modified with sulfonic acid groups of the first embodiment of the present invention.

Fig. 11 shows a support 200 surface-modified with sulfonic acid groups according to a second embodiment of the present invention.

Detailed Description

Catalyst composition

One embodiment of the present invention relates to a catalyst composition for preparing polyketone compounds, characterized by comprising: an onium salt compound having 5 to 40 carbon atoms, including a support surface-modified with a sulfonic acid group or a carboxylic acid group; and a palladium-based catalyst.

Thus, the present invention can provide a catalyst composition exhibiting high activity and preventing fouling in the preparation of polyketone and a palladium mixed catalyst system comprising the same, and can also provide a method for preparing polyketone compounds capable of preventing fouling and omitting the addition of seeds, and having good stability and activity at the time of polymerization reaction, and polyketone polymers prepared therefrom having high apparent density, by using the above mixed catalyst system.

In particular, the catalyst composition for preparing polyketone and the palladium mixed catalyst system using the same of the present invention can prevent fouling occurring in the existing catalyst system for preparing polyketone and improve the reaction activity to a good level, and adopt a non-seeded process without adding a separate seed, and thus can prepare polyketone polymers excellent in apparent density.

(support surface-modified with sulfonic acid group)

The above-mentioned support surface-modified with sulfonic acid groups is included as a heterogeneous (hetero) material of palladium-based catalysts. As used herein, the term "heterogeneous material" refers to the ingredients contained in the catalyst composition, i.e., the material that is present in a state of being mixed with the palladium-based catalyst.

In this case, for example, the catalyst composition of the present invention in the form of mixing a support surface-modified with a sulfonic acid group and a palladium-based catalyst is in a state distinguished from a catalyst in the form of a palladium-based catalyst supported on a support surface-modified with a sulfonic acid group, and when applied to a polyketone polymerization process or the like, the shape and size of the finally prepared polyketone can be uniformly controlled, whereby the apparent density of the polyketone can be improved, a fouling phenomenon occurring in the process can be prevented, and the stability and activity of the polymerization reaction can be improved.

In the above catalyst composition, the equivalent ratio of the support surface-modified with a sulfonic acid group and the above palladium-based catalyst may be 1:0.1 to 1:10, specifically, may be 1:0.1 to 1: 2. More specifically, the equivalence ratio may be 1:0.1 to 1: 1.2. When polyketone polymerization using the catalyst composition is carried out within the above range, the occurrence of fouling can be prevented and higher catalytic activity and high apparent density of the polyketone polymer can be obtained.

The support surface-modified with a sulfonic acid group and the above-mentioned palladium-based catalyst may be included in the above-mentioned catalyst composition in the form of being dispersed in a solvent. Specifically, the above solvent may be an alcohol solvent, more specifically, an alcohol compound having 1 to 20 carbon atoms, such as methanol. When such a catalyst composition is applied to polyketone polymerization, the reactivity can be further improved, and the post-treatment process can be facilitated due to the low boiling point.

The above-mentioned support surface-modified with sulfonic acid groups can uniformly control the shape and size of polyketone to be polymerized, prevent fouling from occurring in polymerization, and serve to further improve the apparent density of polyketone particles formed.

In particular, the sulfonic acid group of the above-mentioned support surface-modified with a sulfonic acid group interacts with the palladium-based catalyst during polymerization to more effectively prevent fouling, form polyketone in the form of powder having a high apparent density, do not adversely affect the activity of the palladium-based catalyst, and are excellent in the effect of maintaining high catalytic activity.

Specifically, the above-mentioned support surface-modified with sulfonic acid groups may include a structure in which functional groups represented by one of the following chemical formulas 1-1 to 1-3 are bonded to the surface of the support.

[ chemical formula 1-1]

*-SO₃H

In the above chemical formula 1-1, a means a moiety bonded to the surface of the support.

[ chemical formulas 1-2]

In the above chemical formula 1-2, R²¹To R²⁶Each independently is hydrogen or C1-C20 alkyl; refers to the moiety bonded to the surface of the support.

[ chemical formulas 1-3]

In the above chemical formulas 1 to 3, R³¹To R³⁴Each independently is hydrogen or C1-C20 alkyl; refers to the moiety bonded to the surface of the support.

Specifically, in the above chemical formulas 1-1 to 1-3, may be a bonding site that is linked to the surface of the support to form a C-C bond or a Si-C bond. In this case, the support and the functional group represented by one of the above chemical formulas 1-1 to 1-3 are connected through a C-C bond or Si-C bond having high bonding strength, and thus, the stability is high and the fixing force to the support can be improved.

The above-mentioned carrier is a porous particle containing pores, and the surface area, pore radius, pores, volume, etc. of the polyketone can be controlled during the polymerization reaction.

The carrier may include one or more of silica, Zeolite, graphite, carbon black, graphene, carbon nanotube, activated carbon, polystyrene, microporous Organic network polymer (microporous Organic network), Metal-Organic Framework (MOF), Zeolite-imidazole Framework (ZIF), Covalent Organic Framework (COF), and biopolymer (biopolymer) including cellulose. In this case, while the shape and size of the polyketone are uniformly controlled during the polymerization reaction, the effect of preventing fouling can be further improved, and the catalyst composition and the polyketone prepared therefrom are good in handling properties and can have more favorable characteristics for the post-treatment process.

Specifically, the support may include one or more of silica, a zeolite imidazolate framework, polystyrene, and a microporous organic network polymer (microporous organic network). In this case, not only the shape and size of the polyketone are controlled, but also the effect of preventing fouling can be further improved, and the commercial utility can be further improved.

When a microporous organic network polymer (microporous organic network) is used as the above-mentioned carrier, the type thereof is not particularly limited. For example, the above microporous organic network polymer may be an organic network polymer formed by a sonogashira coupling reaction using a compound having two or more triple bonds at a terminal and/or a compound having a leaving group (leaving group) at a terminal, a suzuki coupling reaction, or a known cross-coupling reaction in addition thereto.

The above-mentioned leaving group may be a leaving group for sonogashira coupling reaction, suzuki coupling reaction or a known cross-coupling reaction other than the sonogashira coupling reaction, but the present invention is not limited thereto. Specifically, the leaving group (X) may be a leaving group including a halide (halide), tosylate (tosylate), triflate (triflate), mesylate (mesylate), boronic acid (boronic acid), boronate, -N²⁺X^-And the like, which are useful in the coupling reaction. For example, the compound including the leaving group may be a dinitrogen compound (R-N)²⁺) Dialkyl ether compound (R-OR)₂ ⁺) Triflate compoundCompound (R-OSO)₂R^F) Tosylate compound (R-OTf), halide (R-Cl, R-Br, R-I, R-F), mesylate compound (R-OMs), nitrate compound (R-ONO)₂) Phosphate compound (R-OPO (OH))₂) Thioether compounds (R-SR)₂ ⁺) The carboxylic acid compound (R-OCOR), or the compound comprising two or more leaving groups may be R-N₂X、R-OSO₂R、R-OSO₂F、SO₂-R、SOR、R-SR、IPhX、IROTf、I(OH)OTs、RCOCl、R-SO₂-Cl、R-N²⁺X^-、R-OSO₂CF₃、R-OSO₂-Rf、R-OSO₂CH₃、Ar-Ar-I⁺、R-OPO(OR)₂、PF^6-、R-B(OR)₂、R₂N-H、R-X、RCO(SEt)、RCO(SEt)Ar-SMe、RC≡CH、Ar-N₂X、R(C＝O)R₂R-HC-O, R-HC-O, and the like.

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

In a specific embodiment, the compound including a leaving group may be a compound represented by the following chemical formula a.

[ chemical formula A ]

(X-R¹⁰)_p(Z)

In the above chemical formula A, R¹⁰Is an alkylene group having 1 to 20 carbon atoms or an arylene group having 1 to 20 carbon atoms, X is each independently acetylene (ethylene), a halogen group, a boric acid ester group or a trifluoromethanesulfonate group, Z is a carbon atom, a nitrogen atom or a hydrocarbon having 3 to 10 carbon atoms, and p is 2 to 6.

For example, the compounds may be in the form of a skeleton structure represented by the following chemical formulae a1 to a4, respectively.

[ chemical formula A1]

[ chemical formula A2]

[ chemical formula A3]

[ chemical formula A4]

In the above chemical formulas a1 to a4, X is each independently acetylene (ethyl ne), a halogen group, a boric acid ester group, or a trifluoromethanesulfonate group, and Z is a carbon atom, a nitrogen atom, or a hydrocarbon having 3 to 10 carbon atoms. At this time, the hydrocarbon having 3 to 10 carbon atoms may be a cyclic hydrocarbon or a stereostructure hydrocarbon. For example, in example a4, Z may be a tetravalent bonded adamantane structure.

Also, for example, when the compounds represented by the above chemical formulae a1 and a2 are used as reactants, it is easy to supply and receive raw materials, and the cost is low, and thus, when applied to a large-scale production process, the economy can be improved.

Specifically, the average particle diameter of the carrier may be 0.01 μm to 5 μm, more specifically, may be 0.05 μm to 2 μm or 0.45 μm to 1.8 μm. Within the above range, the shape and size of the polyketone can be more uniformly controlled, and the apparent density can be improved. For example, the average particle size of the carrier may be adjusted according to the shape and size of the polyketone particles desired.

In particular, the surface area of the support may be 5m²G to 2000m²A/g, more specifically, may be 20m²(g is 1800 m)²/g，30m²G to 1700m²G or 30m²G to 900m²(ii) in terms of/g. Within the above range, the more preferable range isThe shape and size of the polyketone are uniformly controlled, and the apparent density can be improved. For example, the surface area of the support may be adjusted according to the shape and size of the polyketone particles desired.

Specifically, the average pore radius of the support may be 0.1nm to 25nm, more specifically, may be 0.5nm to 10nm, or 1nm to 6 nm. Within the above range, the shape and size of the polyketone can be more uniformly controlled, and the apparent density can be improved. For example, the average pore radius of the carrier may be adjusted according to the shape and size of the polyketone particles desired.

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

Specifically, the carrier may contain an aromatic ring in the structure. In this case, the stability of the support is good, and when the surface modification is performed with a sulfonic acid group, excellent surface modification efficiency can be achieved.

In the first embodiment, the support surface-modified with sulfonic acid groups may be a hollow structure comprising a microporous organic network polymer (microporous organic network) having repeating units represented by the following chemical formulae 1 to 4.

[ chemical formulas 1 to 4]

In the above chemical formulas 1 to 4, A is a linking site of an atom.

Fig. 10 exemplarily shows the support 100 surface-modified with a sulfonic acid group of the above-described first embodiment. Referring to fig. 10, a support 100 surface-modified with sulfonic acid groups of the first embodiment is a hollow structure 101 composed of a hollow (hollow) structure having a hollow internal space 102, and the hollow structure 101 may be formed of a microporous organic network polymer (microporosity organic network) having repeating units represented by the above chemical formula 1 to 4. For example, in the above hollow structural body 101, a of one repeating unit represented by the above chemical formula 1 to 4 and a of another repeating unit represented by the chemical formula 1 to 4 are connected by a single bond to form an organic network, and micropores (microporus) are included therein.

In addition, the hollow structure 101 of fig. 10 may use a zeolite imidazolate framework or the like as a template (template) for allowing the microporous organic network polymer having the repeating units represented by the above chemical formulas 1 to 4 to have a hollow structure. In this case, the support 100 surface-modified with sulfonic acid groups may include a microporous organic network polymer and a zeolitic imidazolate framework as a support. Also, the zeolitic imidazolate framework used as the template may be used in a state of being removed by an etching process or the like.

Although the structure of the hollow structural body 101 is represented in a spherical shape for convenience of expression in fig. 10, the shape thereof is not limited as long as it has a hollow structure, and for example, the hollow structural body 101 may have a polyhedral shape with an empty internal space.

In a second embodiment, the above-mentioned support surface-modified with sulfonic acid groups may include a silica support, and a microporous organic network polymer (microporous organic network) layer formed on the surface of the above-mentioned silica support and having repeating units represented by the following chemical formulae 1 to 5.

[ chemical formulas 1 to 5]

In the above chemical formulas 1 to 5, a ' independently represents a linking site of an atom bonded to a carrier or a linking site between repeating units, at least one of the above a ' is a linking site of an atom bonded to a carrier, and at least one of the above a ' is a linking site between repeating units.

Fig. 11 shows a support 200 surface-modified with sulfonic acid groups of the above-described second embodiment. Referring to fig. 11, the support 200 surface-modified with sulfonic acid groups of the second embodiment includes a silica support 202 and a microporous organic network polymer layer 201 formed on the surface of the silica support. The above microporous organic network polymer layer 201 is formed of a microporous organic network polymer having repeating units represented by the above chemical formulas 1 to 5, and the support 200 surface-modified with sulfonic acid groups of the above second embodiment may have a form in which the inside of the microporous organic network polymer layer 201 is filled with a silica support 202. For example, the above-mentioned microporous organic network polymer layer 201 includes a polymer having repeating units represented by chemical formulas 1 to 5, at least one a ' of one repeating unit is connected to a ' of an adjacent repeating unit by a single bond to form an organic network, and at least one a ' forms an Si — C bond with the silica support 202.

Also, the microporous organic network polymer layer 201 in fig. 11 may have the microporous organic network polymer layer 201 having the repeating units represented by the above chemical formulas 1 to 5 formed on the surface of the silica support 202 by using silica as a template (template). In this case, the support 200 surface-modified with sulfonic acid groups may include a microporous organic network polymer and silica as a support.

In fig. 11, although the structure of the silica carrier 202 is represented by a spherical structure for convenience of expression, the shape thereof is not particularly limited, and may include a polyhedral shape, for example.

In a third embodiment, the above-mentioned support surface-modified with sulfonic acid groups may include a polystyrene compound having repeating units represented by the following chemical formulas 1 to 6.

[ chemical formulas 1 to 6]

In the above chemical formulas 1 to 6, R⁶Is a sulfonic acid group, a p-toluenesulfonate group or a benzenesulfonic acid group, and n is 10 to 20,000.

In this case, the catalyst composition can make the polyketone particles finally produced more fine and further improve the apparent density and uniformity.

Also, the polystyrene compound may be a copolymer including repeating units represented by the above chemical formulas 1 to 6. For example, the polystyrene compound may be a copolymer of the repeating units represented by the above chemical formulas 1 to 6 and divinylbenzene.

In a fourth specific example, the above-mentioned support surface-modified with sulfonic acid groups may have a structure in which a silica support and a functional group Si-C represented by one of the above-mentioned chemical formulas 1-2 to 1-3 are bonded. In this case, the stability of the catalyst composition is more improved, and the effect of preventing fouling can be further improved.

For example, the above-mentioned support surface-modified with sulfonic acid groups may be prepared by adding sulfuric acid or chlorosulfonic acid to the support.

The method for preparing a support surface-modified with sulfonic acid groups may include a step of preparing a support and a step of sulfonating (sulfonating) the surface of the support to perform surface modification with sulfonic acid groups.

As described above, the support may include one or more of silica, zeolite, graphite, carbon black, graphene, carbon nanotube, activated carbon, polystyrene, microporous organic network polymer (MOF), Zeolite Imidazolate Framework (ZIF), Covalent Organic Framework (COF), and biopolymer containing cellulose (biopolymer). The carrier can be a commercial product or directly prepared. In this case, while the shape and size of the polyketone are uniformly controlled during the polymerization reaction, the effect of preventing fouling can be further improved, and the handling properties of the catalyst composition and the polyketone prepared therefrom can be further improved.

Specifically, the support may include one or more of silica, a zeolite imidazolate framework, polystyrene, and a microporous organic network polymer (microporous organic network). In this case, not only the shape and size of the polyketone are controlled, but also the effect of preventing fouling can be further improved, and economic efficiency is also better.

Specifically, the step of preparing the support may include a step of reacting the prepared support with a compound represented by chemical formula 5 or chemical formula 6 below, after preparing the support. Thereby, a structure including an aromatic ring on the surface of the support can be formed to further improve the efficiency of surface modification of the support with sulfonic acid groups and further improve the bonding force between the sulfonic acid groups and the support.

[ chemical formula 5]

Ar-X₂

[ chemical formula 6]

Ar-Mg-X

In the above chemical formulas 5 to 6, Ar is benzyl or phenyl, Mg is magnesium, and X is halogen.

Specifically, in the above chemical formulas 5 to 6, for example, the halogen may be Cl, Br, F or I, and more specifically, may be I, Cl or Br. In this case, it is economical because raw materials can be easily supplied and received, and the reaction rate can be further improved.

In a specific example, in the step of preparing the carrier, tetrakis- (4-ethynylphenyl) -methane (tetra- (4-ethylphenyl) -methane) and the compounds represented by the above chemical formulas 1 to 6 may be reacted in Pd (PPh) by using a zeolite imidazolate framework as a template₃)₂Cl₂And a method for generating reaction under a CuI catalyst. In this case, the prepared support is subjected to a step of sulfonating (sulfonating) the surface, and thus a support surface-modified with sulfonic acid groups, which is a hollow structure including a microporous organic network polymer having repeating units represented by the above chemical formulas 1 to 4, may be provided.

In another embodiment, in the step of preparing the carrier, tetrakis- (4-ethynylphenyl) -methane (tetra- (4-ethylphenyl) -methane) and the compounds represented by the above chemical formulas 1 to 6 may be reacted in Pd (PPh) by using silica as a template₃)₂Cl₂And a method for generating reaction under a CuI catalyst. In this case, the prepared support is subjected to a step of sulfonating (sulfonating) the surface, and thus may beTo provide a support surface-modified with sulfonic acid groups, comprising a silica support and a microporous organic network polymer (microporous organic network) layer formed on the surface of the silica support and having repeating units represented by the above chemical formulas 1 to 5.

In still another embodiment, the step of preparing the support may include the steps of dispersing the support subjected to dehydration treatment in a solvent, and then adding the compound represented by the above chemical formula 5 to cause a reaction, and bonding an aromatic functional group to the surface of the support. In this case, the surface modification efficiency and the support stability in the sulfonation (sulfonation) step can be further improved.

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

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

For example, when the above support is silica and Ar is benzyl group in chemical formula 5, the prepared support is subjected to a step of sulfonating (sulfonation) the surface, so that a support surface-modified with sulfonic acid group having a structure in which the silica support and the functional group Si — C represented by chemical formula 1-2 are bonded can be provided.

For example, when the above support is silica and Ar is phenyl in chemical formula 5, the prepared support is subjected to a step of sulfonating (sulfonation) the surface, so that a support having a structure in which a silica support and functional groups Si — C represented by the above chemical formulas 1 to 3 are bonded, the surface of which is modified with sulfonic acid groups, can be provided.

The step of sulfonating (sulfonating) the surface of the support to perform surface modification with a sulfonic acid group may include a step of adding sulfuric acid or chlorosulfonic acid to the prepared support to sulfonate (sulfonating).

Specifically, in the step of surface modification with a sulfonic acid group, the prepared above-mentioned carrier may be treated with sulfuric acid (95%) or chlorosulfonic acid to initiate sulfonation on the benzene ring in the structure contained in the carrier. Thus, each of the above supports is modified to have a functional group having a structure containing a sulfonic acid group on the terminal benzene ring.

When a support surface-modified with sulfonic acid groups is prepared by this method, the conversion (surface modification rate) of the support by sulfonation is excellent. Also, even under extreme reaction conditions for treating concentrated sulfuric acid or chlorosulfonic acid, the formed C-C bond or Si-C bond is not broken, and thus a form in which most functional groups are immobilized on the surface of the support can be achieved.

In one embodiment, sulfonation of the support may be performed by the reaction of the following reaction formula 1.

[ reaction formula 1]

In another embodiment, the aromatic sulfonation of the support may be carried out by a reaction of the following equation 2 or equation 3.

[ reaction formula 2]

[ reaction formula 3]

For example, as shown in the above reaction formulas 2 to 3, when an aromatic ring is attached to a support and then sulfonated to perform surface modification, the bonding force between a surface-modifying group and the surface of the support is more excellent, compared to a method of reacting an organic substance with a hydroxyl group (≡ Si-OH) on the surface of silica to pass through an Si-O bond and perform immobilization. In this case, there is an advantage that the surface-modifying group is not easily desorbed (learing). Therefore, the support surface-modified with sulfonic acid groups prepared by this preparation method has excellent stability and can contribute to achieving high activity at the time of polymerization reaction.

Specifically, the support surface-modified with a sulfonic acid group may contain 0.1mmol-H⁺From g to 3mmol-H⁺Sulfonic acid group per gram. In this case, the efficiency of the polyketone synthesis step by the sulfonic acid group can be further improved.

(onium salt Compound containing carboxylic acid group)

When applied to a polyketone production process, the above onium salt compound containing a carboxylic acid group can more effectively prevent fouling by reducing the reaction rate in the entire polymerization reaction. The above onium salt compound containing a carboxylic acid group is used to achieve a reaction pattern for the palladium mixed catalyst system for preparing polyketone of the present invention different from a sharp increase in reaction speed of an initial polymerization reaction occurring in the existing catalyst system for preparing polyketone.

Thus, the polyketone preparation method of the present invention using the above-described catalyst composition for preparing polyketone and palladium mixed catalyst system can omit a process of controlling reaction pressure, temperature, solvent, reaction time and reaction rate during polymerization reaction, can prevent fouling, and can realize excellent activity. These characteristics provide advantages that are advantageous for use in large scale production processes.

Also, the salt (salt) of the above onium salt compound containing a carboxylic acid group may interact with a palladium catalyst for polyketone polymerization to form a heterogeneous seed (hetereogenous seed) having a very small size by itself, and may control the shape of the polyketone polymer synthesized around the catalyst.

Specifically, the onium salt compound containing a carboxylic acid group is a compound in which the onium salt compound is substituted with a carboxylic acid group, and the onium salt compound may include one or more of a nitrogen group (pnitogen) element, a chalcogen (chalcogen) element, and a halogen (halogen) element, and may be, for example, an ammonium, oxygen, phosphonium, sulfonium compound, or the like.

More specifically, the onium salt compound containing a carboxylic acid group described above can be represented by the following formula 2-1.

[ chemical formula 2]

[Z-COOH]⁺[X]-

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

When the compound represented by the above chemical formula 2 is used as the onium salt compound containing a carboxylic acid group, the effect of increasing the reactivity while preventing the scale formation and the effect of increasing the apparent density of the polyketone compound produced without adding a separate seed can be further improved.

The above-mentioned hydrocarbon group having 1 to 20 carbon atoms is not particularly limited, and for example, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, and the like may be included. In this case, not only can the raw materials be easily supplied and received, but also the effect of increasing the reactivity while preventing the fouling and the effect of increasing the apparent density of the polyketone compound produced without adding a separate seed can be further improved.

In specific embodiments, in the above chemical formula 2, Z may be an aromatic heterocyclic group containing nitrogen, phosphorus or sulfur or a branched heteroalkyl group containing nitrogen, phosphorus or sulfur.

Also, the above hydrocarbon group having 1 to 20 carbon atoms may be independently substituted or unsubstituted, and in this case, for example, the substituent may be an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, a halogen group, or the like.

In the above chemical formula 2, [ X ] -is an anion (anion) containing halogen, oxygen, boron, phosphorus, sulfur or a combination thereof, capable of bonding an onium ion substituted with a carboxylic acid group.

Specifically, for example, [ X ]]^-May be a halogen anion including an anion such as chlorine, bromine or iodine; oxyanions including borate, sulfonate, carbonate, nitrate, sulfate, nitrite, phosphate, phosphite, sulfite, tosylate, etc.; an anion comprising a boron atom; an anion comprising a phosphorus atom; comprising tetrafluoroboric acidSalt anion, tetraarylborate anion (aryl is pentafluorophenyl (Ar ═ C)₆F₅) Sulfonic acid anion, p-toluenesulfonic acid anion, trifluoroacetic acid anion, trifluoromethanesulfonic acid anion, hexafluorophosphoric acid anion, ClO₄ ^-、ClO₃ ^-、ClO₂ ^-、ClO^-、BrO₄ ^-、BrO₃ ^-、BrO₂ ^-、BrO^-、IO₄ ^-、IO₃ ^-、IO₂ ^-、IO^-、CO₃ ^2-The plasma contains two or more anions selected from halogen, oxygen, boron, phosphorus and sulfur.

Also, the above anion (anion) containing halogen, oxygen, boron, phosphorus, sulfur or a combination thereof may be independently substituted or unsubstituted, and in this case, 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 may be exemplified as the substituent.

For example, the compound represented by the above chemical formula 2 may include glycine betaine hydrochloride (glycine betaine), trigonelline hydrochloride (trigonelline hydrochloride), 3- (carboxymethyl) -1-mesityl-1H-imidazole-3-bromide (3- (carboxymethyl) -1-mesityl-1H-imidazole-3-ium bromide), 3- (carboxymethyl) -1- (2,6-diisopropylphenyl) -1H-imidazole-3-bromide (3- (carboxymethyl) -1- (2,6-diisopropylphenyl) -1H-imidazole-3-ium bromide), 3- (carboxymethyl) -1-methyl-1H-imidazole-3-bromide (3- (carboxymethyl) -1-methyl-1H-imidazole-3-ium bromide), and combinations thereof 3-ium bromide), 3- (carboxymethyl) -1-methyl-1H-benzo [ d]Imidazole-3-bromide (3- (carboxyymethyl) -1-methyl-1H-benzol [ d)]Imidazol-3-ium bromide), 1- (carboxymethyl) pyridine-1-bromide (1- (carboxyymethyl)_pAvidin-1-ium bromide), 4-carboxy-1-methylpyridine-1-chloride (4-carboxy-1-methylpyridine-1-ium chloride), 3- (carboxymethyl) -1-mesityl-1H-imidazole-3-chloride (3- (carboxymethyl) -1-mesityl-1H-imidozol-3-ium chloride), 2-carboxy-N, N, N-trimethylethan-1-ammonium bromide (2-carboxy-N, N, N-trimethylethan-1-amide bromide), and (3-carboxypropyl) triphenylphosphine ((3-carbopxypropyl) triphnylon bromide). When the above-exemplified compounds are used as the onium salt compound containing a carboxylic acid group, the effect of increasing the reactivity while preventing the scale formation and the effect of increasing the apparent density of the polyketone compound produced without adding a separate seed can be further improved.

May be at 0.1 × 10^-3M to 1.0X 10^-3The molar concentration of M comprises the onium salt compound comprising a carboxylic acid group described above. In this case, in the polyketone production process, the polymerization stability and the degree of activation are further improved, and the polyketone compound can be produced in an excellent yield.

(Palladium-based catalyst)

As the palladium-based catalyst used in the present invention, there is no particular limitation as long as it is a conventional palladium-based catalyst that can be used for polyketone polymerization.

The palladium-based catalyst is used in a form not supported on a carrier or the like. Further, the palladium-based catalyst is not used in the form previously supported on the carrier surface-modified with a sulfonic acid group, but is added in a state of being separated alone at the time of polymerization. In this case, it is possible to reduce the loss of activity of the palladium-based catalyst and to reduce fouling more effectively.

The palladium-based catalyst may be a Pd catalyst used for polyketone polymerization.

The palladium-based catalyst may be a catalyst represented by one of the following chemical formulas 3 to 5.

[ chemical formula 3]

[ chemical formula 4]

[ chemical formula 5]

In the above chemical formulas 3 to 5, R¹To R⁴Each independently hydrogen, alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms or aromatic hydrocarbon group having 6 to 20 carbon atoms, Y¹And Y²Each independently being a halogen anion or an oxyacetate anion, Y³To Y⁵Each independently hydrogen, alkyl having 1 to 10 carbon atoms, organosilyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 10 carbon atoms or aromatic hydrocarbon group having 6 to 20 carbon atoms, Y⁶Is an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms.

Specifically, the above Y³To Y⁵And Y⁶Each of which may be substituted or unsubstituted and may or may not contain one or more heteroatoms and, in the case of cyclic structures, may be monocyclic or polycyclic structures.

The palladium-based catalyst may be used as dispersed in a polymerization solvent (for example, an alcohol solvent). For example, a palladium-based catalyst dispersed in a polymerization solvent may be added to a reactor, followed by stirring and adding an olefin gas and a carbon monoxide gas at room temperature to carry out saturation, and a copolymerization reaction of an olefin and carbon monoxide may be carried out by raising the temperature of the reactor.

In the polymerization reaction of the olefin and carbon monoxide, the palladium-based catalyst represented by one of the above chemical formulas 3 to 5 can increase the copolymerization activity of the olefin and carbon monoxide, and can prepare polyketone compounds.

The above palladium-based catalyst is not particularly limited, and may be, for example, one selected from the group consisting of 1, 3-bis (2-o-methoxyphenylphosphine) propane]Pd(OAc)₂(1,3-Bis(di-o-methoxyphenylphosphino)propane]Pd(OAc)₂) Catalyst, Pd (2-o-methoxyphenyl phosphine) (bis-diphenylphosphinopropane) (OAc)₂(Pd(di-o-methoxyphenylphosphino)(diphenylphosphino)propane)(OAc)₂) Catalyst and Pd (1)3-bis diphenylphosphinopropane) (OAc)₂(Pd(1,3-bis(diphenylphosphino)propane)(OAc)₂) One or more of the group consisting of catalysts. In this case, the copolymerization reactivity and activity of the olefin and carbon monoxide are more favorable, and the effect of preventing the scale formation phenomenon by the interaction with the onium salt compound containing a carboxylic acid group can be further improved. In this case, not only the activity is excellent, but also the fouling phenomenon can be further prevented and polyketone can be formed which is uniformly and alternately polymerized.

In particular, when the above-exemplified catalyst is used, the effect of adjusting the morphology (morphology) of polyketone polymer synthesized around the catalyst by self aggregation of the salt (salt) and palladium catalyst can be further improved.

Specifically, the solvent of the above catalyst system may be an alcohol solvent, more specifically, an alcohol compound having 1 to 20 carbon atoms, and for example, methanol may be used. In this case, the polyketone production process has higher reactivity and activity, and a low boiling point, and therefore, may be advantageous for the post-treatment process.

Catalyst composition for preparing polyketone compounds

Yet another embodiment of the present invention relates to a palladium mixed catalyst system for the preparation of polyketones, characterized in that it comprises the above catalyst composition for the preparation of polyketones, using olefins and carbon monoxide as reactants. In this case, the specific contents of the catalyst composition are the same as those described above.

Process for preparing polyketone

The polyketone preparation method according to an embodiment has a form in which the above-described support surface-modified with a sulfonic acid group is mixed with a palladium-based catalyst as a heterogeneous material, for example, a state of a catalyst having a form different from that in which a palladium-based catalyst is supported on a support surface-modified with a sulfonic acid group, and thus, when applied to a polyketone polymerization process or the like, uniformly controls the shape and size of finally prepared polyketone, thereby improving the apparent density of polyketone and preventing a fouling phenomenon occurring in the process, and achieving the effect of improving the stability and activity of the polymerization reaction.

According to another embodiment of the polyketone production method, the salt of the above onium salt compound containing a carboxylic acid group and the palladium catalyst interact to aggregate together to produce a heterogeneous seed of a minute size in the reaction solution, at which the size of the aggregate formed is small, about 100nm, so that the particle size and morphology of the polyketone polymer formed can be controlled and the apparent density can be increased. The polyketone preparation method of the invention realizes high apparent density to the extent that the existing method of adding heterogeneous seeds is difficult to obtain, not only omits the addition of seeds, but also improves the activity only through additives and prevents scaling.

As described above, when polyketone is polymerized using the catalyst composition of the present invention, fouling can be prevented, and the particle shape of the polyketone produced can be adjusted according to the morphology of the modified support. In this case, polymer particles having a high apparent density can be produced, and thus productivity can be improved.

The specific contents concerning the onium salt compound and the palladium-based catalyst used in the specific preparation method of polyketone, which comprises a support surface-modified with a sulfonic acid group or a carboxylic acid group and has 5 to 40 carbon atoms, are the same as those described above.

The solvent at the time of polymerization may be an alcohol compound having 1 to 20 carbon atoms.

In the polymerization reaction, the amount of the catalyst may be 0.1X 10^-3M to 1.0X 10^-3The molar concentration of M includes the palladium-based catalyst described above. In this case, the polymerization stability and the degree of activation of the polyketone production process can be further improved, and the polyketone compound can be produced in good yield.

In the polymerization ofWhen reacting, the amount of the catalyst may be 0.1X 10^-3M to 1.0X 10^-3The molar concentration of M includes the above-described support surface-modified with a sulfonic acid group or an onium salt compound of a carboxylic acid group. In this case, the polymerization stability and the degree of activation of the polyketone production process can be further improved, and the polyketone compound can be produced in good yield.

In a specific embodiment, when the above catalyst composition for preparing polyketone comprises a support surface-modified with a sulfonic acid group, the polyketone preparation method may further comprise a step of preparing a support surface-modified with a sulfonic acid group by adding sulfuric acid or chlorosulfonic acid to the support. At this time, the specific contents regarding the method for preparing the support surface-modified with sulfonic acid groups are the same as those described above.

For example, the olefin may be ethylene, propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, cyclopentene, norbornene, dicyclopentadiene, cyclooctene, cyclododecene, styrene, α -methylstyrene, alkyl (meth) acrylic acid, alkyl (meth) acrylate, or the like. The above-mentioned olefins may be used singly or in combination of two or more.

More specifically, ethylene, propylene, hexene, and decene may be used alone or in combination. In this case, the activity and the yield of the polyketone polymer can be further improved because of excellent interaction with the catalyst.

In one embodiment, when 1 to 4 parts by weight of propylene is mixed with 100 parts by weight of ethylene for use, the melting temperature of the polyketone produced can be lowered and a good heat denaturation temperature can be achieved.

Specifically, the molar ratio of the olefin to the carbon monoxide may be 95:5 to 5:95, more specifically 5:1 to 1: 5. In this case, the reactivity of the polyketone production process can be further improved.

Specifically, the content ratio of the olefin to the carbon monoxide may be 10 to 20 bar to 30 to 40 bar. In this case, the reactivity of the polyketone production process can be further improved.

Specifically, the equivalent ratio of the onium salt compound including the above-mentioned support surface-modified with a sulfonic acid group or the above-mentioned carboxylic acid group and the above-mentioned palladium-based catalyst may be 1:0.1 to 1: 10. In this case, the reactivity and yield of the polyketone production process can be further improved.

In a specific embodiment, the equivalent ratio of the above palladium-based catalyst and the support surface-modified with a sulfonic acid group to the above palladium-based catalyst may be 1:0.1 to 1.2, more specifically, the equivalent ratio may be 1:0.1 to 1: 1.2. When polyketone polymerization using the catalyst composition is carried out within the above range, the occurrence of fouling can be prevented and higher catalytic activity and high apparent density of the polyketone polymer can be obtained.

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

Specifically, the reaction temperature may be maintained in the range of 50 ℃ to 150 ℃, more specifically, 70 ℃ to 130 ℃. In this case, the reactivity of the polyketone production process can be further improved.

In particular, since carbon monoxide and some olefins are gases at the above temperatures, the polymerization reaction can be carried out in a pressure reactor. In this case, the reactivity and the degree of activation of the polyketone production process can be further improved.

Specifically, the reactor internal pressure may be 200atm or less, more specifically 100atm or less. In this case, the reactivity and the degree of activation of the polyketone production process can be further improved.

Specifically, in the above polyketone production method, the above palladium mixed catalyst system for producing polyketone may be present in a state of being dispersed in a solvent to catalyze a polymerization reaction.

Specifically, the solvent may be an alcohol solvent, more specifically, an alcohol compound having 1 to 20 carbon atoms, and for example, methanol may be used. In this case, the polyketone production process has higher reactivity and activity, and a low boiling point, and therefore, may be advantageous for the post-treatment process.

In one embodiment, the above-described carrier surface-modified with sulfonic acid groups is insoluble in an organic solvent and thus may be present in the form of a slurry.

In another embodiment, the polyketone production process using the onium salt compound comprising a carboxylic acid group described above can be a seedless process.

Polyketone polymers

Still another embodiment of the present invention relates to a polyketone polymer formed by the method according to the above polyketone preparation.

In a specific embodiment, the polyketone polymer formed by the above polyketone preparation method may be prepared by allowing the above support surface-modified with sulfonic acid groups as a heterogeneous material to interact with a palladium-based catalyst, and may have an improved apparent density.

In another embodiment, the morphology of the polyketone polymer formed by the polyketone preparation method described above can be controlled by the heterogeneous seeds of fine size formed by the interaction and simultaneous coagulation of the salt of the onium salt compound containing a carboxylic acid group and the palladium catalyst described above. At this time, the size of the formed aggregate is small, about 100nm, and therefore, the apparent density of the formed polyketone polymer may be large, and may be about 0.1g/ml to 0.5g/ml, for example, about 0.27g/ml to 0.47 g/ml.

Examples

Hereinafter, the constitution and action of the present invention will be described in more detail by way of examples of the present invention. It should be understood, however, that this is by way of illustration and example only and should not be construed to limit the invention in any way.

Preparation example 1 preparation of a support surface-modified with sulfonic acid group

(preparation carrier)

500mL of Methanol (Methanol) and 90mL of H were added₂O, 32mL of Ammonium hydroxide solution (Ammonium hydroxide solution) and 1.2g of cetyltrimethyl bromideAmmonium Chloride (CTAB) was added sequentially to a 1L beaker and stirred at 300RPM for 30 minutes. Tetraethyl orthosilicate (TEOS) was added while stirring at 300 RPM. The reaction was carried out at room temperature for 24 hours while stirring at 300 RPM. The silica (Si lica) synthesized was separated by centrifuge, washed with methanol and dried in an oven. The dried silica was then calcined at 550 ℃ for 5 hours. The prepared calcined silica was finely ground in a mortar and heated at 850 ℃ for 12 hours in an Ar furnace to prepare a carrier.

Benzyl magnesium chloride (benzyl magnesium chloride) was added to the silica support prepared above, and stirred at room temperature under a nitrogen atmosphere to cause a reaction, thereby performing a surface treatment to attach a benzyl group to the surface of the silica support.

(sulfonation)

Sulfuric acid was added to the silica support having benzyl groups attached thereto prepared as described above, and stirred at room temperature overnight to prepare a support (1.8 μm SiO) surface-modified with sulfonic acid groups₂-SO₃H) In that respect The thus prepared support surface-modified with sulfonic acid groups was confirmed by SEM photograph, and the result thereof is shown in fig. 1.

Preparation example 2 preparation of a support surface-modified with sulfonic acid group

(preparation carrier)

Zinc nitrate hexahydrate (Zinc nitrate hydrate, 1eq, 0.1mol, 297.49g/mol, 29.75g) was dissolved in 500mL of methanol to prepare a Zinc nitrate solution (Zinc nitrate solution), and hexadecyltrimethylammonium bromide (Hexadecyltrimethyl ammonium bromide; CTAB, 99 +%, 0.25eq, 0.025mol, 364.45g/mol, 9.1g) was dissolved in 125mL of methanol to prepare a solution (CTAB solution). Also, 2-methylimidazole (4eq, 0.4mol, 82.10g/mol, 32.84g) was dissolved in 500mL of methanol to prepare a solution (2-methylimidazole solution).

100mL of the zinc nitrate solution prepared above was added to 250mL of RB (5), and 20mL of CTAB solution and 100mL of 2-methylimidazole solution were sequentially added while stirring at 1100rpm, and further stirred for 5 minutes. Thereafter, the stirring was stopped, and the mixture (room temperature) was allowed to stand without shaking for 18 hours, and then the supernatant was discarded, and the prepared ZIF-8 was separated by a centrifuge. The separated ZIF-8 carrier was washed twice with methanol, dried with a Vacuum pump (Vacuum pump), and then used as a template.

After flame drying a 100mL Schlenk flask (Schlenk flash), argon was added. Then, Pd (PPh) was sequentially added to the bottle₃)₂Cl₂(10 mol%, 0.024mmol, 701.90g/mol, 0.0168g), CuI (10 mol%, 0.024mmol, 190.45g/mol, 0.0046g), and 0.4g of ZIF-8 as the carrier prepared above. Thereafter, 60mL of Triethylamine (Triethylamine; TEA) was further added thereto and dispersed in a sonicator for 1.5 hours to prepare a dispersion. To the above dispersion was added tetrakis- (4-ethynylphenyl) -methane (tetra- (4-ethylphenyl) -methane, 1eq, 0.24mmol, 416.51g/mol, 0.1g) and 1,4-Diiodobenzene (1,4-Diiodobenzene, 2eq, 0.48mmol, 329.90g/mol, 0.1584g) and again dispersed in the sonicator for 5 minutes. Thereafter, the mixture was allowed to react at 100 ℃ for 24 hours, cooled to room temperature, and the synthesized support in the form of a hollow structure comprising the above-prepared support, i.e., ZIF-8 as a template (ZIF-8@ MON) was separated by a centrifuge. The synthesized carrier was washed twice using Acetone (Acetone), Dichloromethane (dichromethane), Methanol (Methanol) and Acetone (Acetone) in this order, and then dried with a vacuum pump.

Further, the above prepared carrier (ZIF-8@ MON, 0.16g) and 15mL of methanol were added to a Falcon tube and dispersed, and then 20mL of Acetic acid (Acetic acid) was added thereto, and Etching (Etching) was performed while stirring the mixture for 1 hour to further promote the formation of a microporous organic network polymer (microporous organic network) in the carrier. Subsequently, the etched support (HMON) was separated with a centrifuge, washed 10 times with methanol (MeOH), twice with acetone and dried with a vacuum pump for sulfonation.

(sulfonation)

A100 mL schlenk bottle was flame dried and then argon was added. To the above-mentioned bottle, a carrier (HMON) as a hollow structure comprising a microporous organic network polymer (microporous organic network) was added0.04g) and 20mL of methylene chloride and dispersed well. After dispersion, the temperature was lowered to 0 ℃ and 0.6mL of ClSO was added very slowly₃H, the temperature was raised to room temperature and reacted under Ar for 1.5 hours. After the temperature was again lowered to 0 ℃, the remaining ClSO was quenched with methanol₃H. Separating the support surface-modified with sulfonic acid groups by a centrifuge, using methanol and H₂O is expressed as a ratio of 2: the solution mixed at a ratio of 1 was washed at a pH of 7. After washing twice more with methanol, it was dried by vacuum pump.

The prepared support surface-modified with sulfonic acid groups was confirmed by SEM (parts (a) and (b) of fig. 3) and TEM (part (c) of fig. 3) photographs, and the results thereof are shown in fig. 3.

Preparation example 3 preparation of a support surface-modified with sulfonic acid group

(preparation carrier)

To a 250mL round bottom flask was added 200mL Ethanol (Ethanol) followed by 23mL distilled H₂O and 7mL ammonium hydroxide solution (28-30%) and stirred at 300RPM for 30 minutes. Thereafter, 18mL of Tetraethyl orthosilicate (TEOS, 1eq, 0.081mol, 208.33g/mol, 0.933g/mL) was added and the reaction was carried out with rapid stirring at room temperature for 18 hours. After adding 5 drops of acetic acid, 100mL of hexane and 150mL of dichloromethane were added and shaken, and then the coagulated silica was separated with a centrifuge to obtain a mixture of 1:1 ratio of hexane and dichloromethane, the mixture solution was washed three times, heated in an oven at 80 ℃ overnight and dried to prepare a silica support as a template.

After flame drying a 100mL schlenk flask, argon was added. Then, Pd (PPh) was added sequentially₃)₂Cl₂(10 mol%, 0.024mmol, 701.90g/mol, 0.0168g), CuI (10 mol%, 0.024mmol, 190.45g/mol, 0.0046g), and 0.6g of the silica support prepared above. Then, Triethylamine (Triethylamine; TEA, 60mL) was further added, and sufficiently dispersed in an ultrasonograph for 1.5 hours to prepare a dispersion. To the dispersion was added tetrakis- (4-ethynylphenyl) -methane (1eq, 0.24mmol, 416.51g/mol, 0.1g) and 1,4-diiodobenzene (2eq, 0.48mmol, 329.90g/mol, 0.1584g), again under ultrasoundDisperse in the instrument for 5 minutes. Thereafter, after reacting at 100 ℃ for 24 hours, the reaction product was cooled to room temperature, and the synthesized Support (SiO) comprising a silica support as a template and comprising a microporous organic network polymer layer prepared above was separated by a centrifuge₂@ MON). The synthesized carrier was washed twice using Acetone (Acetone), Dichloromethane (dichromethane), methanol and Acetone in this order, and then dried with a vacuum pump.

(sulfonation)

After flame drying a 100mL schlenk flask, argon was added. The above-mentioned bottle was charged with a Support (SiO) comprising a silica support as template and a microporous organic network polymer layer₂@ MON, 0.72g) and 60mL of methylene chloride. After dispersion, the temperature was lowered to 0 ℃ and 1.8mL of ClSO was added very slowly₃H, the temperature was raised to room temperature and the reaction was carried out under Ar for 1.5 hours. After the temperature was again lowered to 0 ℃, methanol was added to quench the remaining ClSO₃H. Separating the support surface-modified with sulfonic acid groups by means of a centrifuge, using Methanol (Methanol) and H₂O is expressed as a ratio of 2: the solution mixed at a ratio of 1 was washed at a pH of 7. After washing twice more with methanol, it was dried by vacuum pump.

Preparation example 4 preparation of a support surface-modified with sulfonic acid group

(preparation of reactants for preparation of the support)

Purification of styrene stabilizers for styrene removal (4-tert-butylcatechol)

30mL of methylene chloride was added to 200mL of styrene. To the above mixed solution was added 50mL of 1M sodium hydroxide solution, and extraction was performed 3 times. After dehydration over magnesium sulfate, methylene chloride was removed by a vacuum pump. Blocked from light and then stored frozen under argon.

Purification of Divinylbenzene stabilizer for removal of Divinylbenzene (4-tert-butylcatechol)

10mL of methylene chloride was added to 80mL of styrene. To the above mixed solution was added 50mL of 1M sodium hydroxide solution, and extraction was performed 3 times. After dehydration over magnesium sulfate, methylene chloride was removed by a vacuum pump. Blocked from light and then stored frozen under Ar.

(preparation carrier)

After flame drying a 100mL single neck schlenk flask, argon was added. After adding distilled water thereto, the above purified Styrene (Styrene) and Divinylbenzene (Divinylbenzene) were added and heated to 65 ℃. After removing the gas from the solution while blowing argon, stirring was carried out for at least 15 minutes until an emulsion was formed. Distilled water in which potassium persulfate was dissolved was added to the above mixed solution and reacted at 65 ℃ for 20 hours. After the reaction, it was put in a refrigerator for 2 hours, and then the temperature was raised to room temperature. After dilution with about 80mL of ethanol, the prepared Polystyrene powder (Polystyrene powder) was separated by a centrifuge, washed 5 times with ethanol and dried by a vacuum pump.

(sulfonation)

After flame drying a 50mL single neck schlenk flask, argon was added. Polystyrene (Polystyrene powder) powder and sulfuric acid (sulfuric acid) were added, followed by sonication for 30 minutes. Stirred at 40 ℃ for at least 18 hours and cooled to room temperature. Diluted with methanol and centrifuged to sink. By mixing methanol and H₂O is expressed as a ratio of 2: the solution mixed at a ratio of 1 was washed at a pH of 7. After washing twice more with methanol, it was dried by vacuum pump.

Preparation example 5 preparation of support without surface modification

The support was prepared in the same manner as in preparation example 2, except that the sulfonation step was omitted.

The physical properties of the carriers prepared in the above preparation examples 1 to 5 are shown in table 1 below.

TABLE 1

Example 1

To 10mL of methanol was added 1.0mg of Pd (1, 3-bis (2-methoxyphenyl) phosphinopropane) (OAc)₂And 2.7mg of the support subjected to surface modification prepared in preparation example 1 above (1.8 μm SiO)₂-SO₃H) To prepare the catalyst composition by mixing at room temperature.

The above catalyst composition was charged into a high pressure reactor (50mL 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 reactor temperature was raised to 90 ℃ and polymerization was carried out for about 15 hours. After the reaction, 4.8g of polyketone powder (activity: 33.84 Kg/g-Pd; 1.29 Kg/g-catalyst, apparent density: 0.297g/mL) were obtained

An SEM photograph taken to recover the sulfonated support used in the reaction prepared in preparation example 1 after preparing polyketone by the method of example 1 described above is shown in fig. 2.

The photograph of the polyketone prepared is shown in FIG. 5, and it was confirmed by naked eyes that no fouling occurred.

Example 2

Except that 1.5mg of Pd (1, 3-bis (2-methoxyphenyl) phosphino propane) (OAc) was added to 10mL of methanol₂And 4.0mg of the support subjected to surface modification prepared in preparation example 1 (1.8 μm SiO)₂-SO₃H) The same procedure as in example 1 above was repeated, except that mixing was performed at room temperature to prepare a catalyst composition. After the reaction, 4.95g of polyketone powder (activity: 23.26 kg/g-Pd; 0.90 kg/g-catalyst, apparent density: 0.309g/mL) was obtained.

Example 3

Except that 0.6mg of Pd (1, 3-bis (2-methoxyphenyl) phosphino propane) (OAc) was added to 20mL of methanol₂And 0.8mg of the support subjected to surface modification prepared in preparation example 2 were carried out in the same manner as in example 1 above. After the reaction, 5.6g of polyketone powder (activity: 61.23 Kg/g-Pd; 4.08 Kg/g-catalyst, apparent density: 0.374g/mL) was obtained.

An SEM photograph taken by recovering the support surface-modified with sulfonic acid groups prepared in preparation example 2 before preparing polyketone by the method of example 3 described above is shown in part (a) of fig. 4.

An SEM photograph taken to recover the support surface-modified with sulfonic acid groups prepared in preparation example 2 used in the reaction after polyketone was prepared by the method of the above example 3 is shown in part (b) of fig. 4.

Referring to FIG. 4, the support surface-modified with sulfonic acid groups of preparation example 2 before the reaction had a diameter of 521nm and a thickness of 20nm, and after the reaction, the diameter was 625nm and the thickness was 120 nm.

Example 4

Except that 1.0mg of Pd (1, 3-bis (2-methoxyphenyl) phosphino propane) (OAc) was added to 10mL of methanol₂And 1.1mg of the support subjected to surface modification prepared in the above preparation example 3 were carried out in the same manner as in the above example 1. After the reaction, 3.7g of polyketone powder (activity: 26.53 kg/g-Pd; 1.86 kg/g-catalyst, apparent density: 0.310g/mL) was obtained.

The photograph of the polyketone prepared is shown in FIG. 7, and it was confirmed by naked eyes that no fouling occurred.

Example 5

Except that 1.5mg of Pd (1, 3-bis (2-methoxyphenyl) phosphino propane) (OAc) was added to 10mL of methanol₂And 1.0mg of the support subjected to surface modification prepared in the above preparation example 4 to carry out mixing at room temperature to prepare a catalyst composition, the rest was carried out in the same manner as in the above example 1. After the reaction, 2.5g of polyketone powder (activity: 11.94 kg/g-Pd; 1.02 kg/g-catalyst, apparent density: 0.318g/mL) was obtained.

Example 6

Except that instead of Pd (1, 3-bis (2-methoxyphenyl) phosphinopropane) (OAc)₂0.8mg of Pd (1, 3-bisdiphenylphosphinopropane) (OAc) was used₂The procedure of example 1 was repeated except for using a palladium catalyst. After the reaction, 0.265g of polyketone powder (activity: 1.89 Kg/g-Pd; 0.135 Kg/g-catalyst, apparent density: 0.389g/mL) was obtained.

Comparative example 1

The same procedure as in example 2 above was conducted except that no support subjected to surface modification was added at the time of preparing the catalyst composition (catalyst activity: 0.478 kg/g-Pd).

Comparative example 2

The same procedure as in example 2 was repeated, except that p-toluenesulfonic acid was added in place of the support subjected to surface modification to cause a reaction. After the reaction, 1.33g of polyketone powder was obtained (activity: 6.27 kg/g-Pd; 0.814 kg/g-catalyst).

A photograph of the polyketone prepared is shown in FIG. 8, and the occurrence of fouling was confirmed with the naked eye.

Comparative example 3

Except that 1.5mg of Pd (dmppp) (OAc) was added to 10mL of methanol₂And 0.4mg of the carrier of preparation example 5 prepared above containing no sulfonic acid group were mixed at room temperature to prepare a catalyst composition, and the rest was carried out in the same manner as in example 2 above (catalyst activity: 0.771 kg/g-Pd).

Comparative example 4

The same procedure as in comparative example 2 above was conducted, except that Amberlyst 15 was added as a support modified with a sulfonic acid group at the time of preparing the catalyst composition. After the reaction, 0.64g of polyketone powder was obtained (activity: 3.01 kg/g-Pd; 0.388 kg/g-catalyst).

A photograph of the polyketone prepared is shown in FIG. 9, and the occurrence of fouling was confirmed with the naked eye.

TABLE 2

Example 7

[1, 3-bis (di-o-methoxyphenylphosphino) propane in a high-pressure reactor (50ml size)]Pd(OAc)₂The catalyst (2. mu. mol) was dispersed in methanol (MeOH, 10ml) and the reactor was assembled and saturated by adding 25 bar of ethylene gas and 35 bar of carbon monoxide (CO) while stirring at room temperature. Thereafter, additives as shown in the following Table 3 were added to the above reactor, and the temperature of the reactor was raised to 90 ℃ to conduct polymerization at 62 bar for about 15 hours. After the completion of the above polymerization reaction, the reaction product was cooled to room temperature, filtered, and dried in an oven at 65 ℃ for 1 hour to obtain polyketone polymer powder.

Examples 8 to 16 and comparative examples 5 to 12

Polymerization was carried out in the same manner as in example 7, except that the composition of the ingredients added to the reaction was changed as shown in the following Table 3.

TABLE 3

The kinds of palladium catalysts used in the above examples 7 to 22 and comparative examples 5 to 12 are as follows.

[ catalyst A ]

1, 3-bis (2-o-methoxyphenyl phosphine) propane]Pd(OAc)₂

[ catalyst B ]

Pd (2-o-methoxyphenyl phosphine) (bis-diphenylphosphinopropane) (OAc)₂

[ catalyst C ]

Pd (1, 3-bis diphenylphosphinopropane) (OAc)₂

[ catalyst D ]

:1,3-Bi s(di-o-methoxyphenylphosphino)_propane]Pd(Cl)₂

The kinds of additives used in the above 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-chloride (3- (carboxymethy) -1-mesityl-1H-imidazole-3-ium chloride)

[ additive 1C ]

Trigonelline hydrochloride (trigonelline hydrochloride)

[ additive 1D ]

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

[ additive 1E ]

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

[ additive 1F ]

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

[ additive 1G ]

1- (carboxymethyl) pyridine-1-bromide (1- (carboxyymethyl) pyridine-1-ium bromide)

[ additive 1H ]

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

[ additive 1I ]

[ additive 1J ]

2-carboxy-N, N, N-trimethylethan-1-ammonium bromide (2-carboxy-N, N, N-trimethylenthan-1-aminium bromide)

[ additive 1K ]

(3-carboxypropyl) triphenylphosphine bromide

[ additive 2]

[ additive 3]

[ additive 4]

[ additive 5]

[ additive 6]

[ additive 7]

The degree of activation of the polymerization reactions carried out in the above examples 7 to 22 and comparative examples 5 to 12 is shown in the following table 4.

TABLE 4

From the above tables 3 and 4, it was confirmed that examples 7 to 22 of the polyketone production method according to the present invention can prevent fouling using an onium salt compound containing a carboxylic acid group as an additive, and are excellent in stability and activity at the time of polymerization reaction.

In contrast, it was confirmed that comparative example 5, which did not include an additive, exhibited very low activity, and fouling occurred in comparative examples 6 and 7, which used p-toluene sulfonic acid (TsOH) as a strong acid as an additive. Further, it was confirmed that comparative examples 8 to 12 using additives 3 to 7 having a completely different structure from the present invention because they did not contain a carboxylic acid group or did not include an onium salt compound had very low activity, and thus it was difficult to sufficiently form a polyketone polymer and fouling occurred.

Simple modifications and variations of the present invention can be easily implemented by those of ordinary skill in the art, and such modifications and variations are considered to be included in the field of the present invention.

Claims

1. a catalyst composition for preparing polyketone compound is characterized in that, comprising:

Onium salt compounds, having 5 to 40 carbon atoms, including a carrier or carboxylic acid group surface-modified with a sulfonic acid group; and

Palladium-based catalyst;

The carrier surface-modified with a sulfonic acid group includes:

(i) A hollow structure of a microporous organic network polymer having repeating units represented by the following Chemical Formulas 1-4:

[Chemical formula 1-4]

where A is the attachment site of the atom;

(ii) a silica support and a microporous organic network polymer layer having repeating units represented by the following Chemical Formulas 1-5 formed on the surface of the silica support:

[Chemical formula 1-5]

wherein A' each independently represents a linking site of an atom bonded to the carrier or a linking site between repeating units, at least one of the A' is a linking site of an atom bonded to the carrier, and the At least one of A' is a linking site between repeating units; or

(iii) Polystyrene modified with sulfonic acid groups.

2 . The catalyst composition for preparing a polyketone compound according to claim 1 , wherein the carrier surface-modified with a sulfonic acid group comprises the following chemical formulas 1-1 to 1-3. 3 . A structure representing a functional group bonded to the surface of the support:

[Chemical formula 1-1] *-SO ₃ H

Among them, * refers to the part bonded to the surface of the carrier;

[Chemical formula 1-2]

Wherein, R ²¹ to R ²⁶ are each independently hydrogen or C1-C20 alkyl; * refers to the part bonded to the surface of the carrier;

[Chemical formula 1-3]

Wherein, R ³¹ to R ³⁴ are each independently hydrogen or C1-C20 alkyl; * refers to the part bonded to the surface of the carrier.

3. The catalyst composition for preparing a polyketone compound according to claim 1, wherein the carrier surface-modified with a sulfonic acid group comprises a Polystyrene compound:

[Chemical formula 1-6]

wherein, R ⁶ is a sulfonic acid group, a p-toluenesulfonic acid group or a benzenesulfonic acid group, and n is 10 to 20,000.

4 . The catalyst composition for preparing polyketone compounds according to claim 2 , wherein the surface-modified carrier with a sulfonic acid group is prepared by combining a silica carrier with the chemical formula 1-2. 5 . It is formed by bonding to the functional group Si-C represented by one of the chemical formulas 1-3.

5 . The catalyst composition for preparing a polyketone compound according to claim 1 , wherein the surface-modified carrier with a sulfonic acid group and the palladium-based catalyst are in the form of being dispersed in a solvent. 6 .

6. The catalyst composition for preparing a polyketone compound according to claim 5, wherein the solvent is an alcohol compound having 1-20 carbon atoms.

7. The catalyst composition for preparing a polyketone compound according to claim 1, wherein the onium salt compound is represented by the following chemical formula 2:

[Chemical formula 2] [Z-COOH] ⁺ [X] ^-

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

8 . The catalyst composition for preparing a polyketone compound according to claim 7 , wherein, in the chemical formula 2, Z is an aromatic heterocyclic group. 9 .

9 . The catalyst composition for preparing a polyketone compound according to claim 7 , wherein, in the chemical formula 2, Z is a branched heteroalkyl group. 10 .

10. The catalyst composition for preparing a polyketide compound according to claim 7, wherein the compound represented by the chemical formula 2 comprises: glycine betaine hydrochloride, trigonelline hydrochloride, 3- (Carboxymethyl)-1-mesityl-1H-imidazole-3-bromide, 3-(carboxymethyl)-1-(2,6-diisopropylphenyl)-1H-imidazole-3 - Bromide, 3-(carboxymethyl)-1-methyl-1H-imidazole-3-bromide, 3-(carboxymethyl)-1-methyl-1H-benzo[d]imidazole-3- Bromide, 1-(carboxymethyl)pyridine-1-bromide, 4-carboxy-1-methylpyridine-1-chloride, 3-(carboxymethyl)-1-mesityl-1H-imidazole - One or more of 3-chloride, 2-carboxy-N,N,N-trimethylethyl-1-ammonium bromide, and (3-carboxypropyl)triphenylphosphine bromide.

11. The catalyst composition for preparing a polyketone compound according to claim 1, wherein the palladium-based catalyst is represented by one of the following chemical formulas 3 to 5:

[Chemical formula 3]

[Chemical formula 4]

[Chemical formula 5]

wherein 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 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 A cycloalkyl group having 3 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, Y ⁶ is an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms Or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms.

12. The catalyst composition for preparing a polyketone compound according to claim 1, wherein the palladium-based catalyst is selected from the group consisting of 1,3-bis(2-o-methoxyphenylphosphine)propane] Pd(OAc) ₂ catalyst, Pd(2-o-methoxyphenylphosphine)(bisdiphenylphosphinopropane)(OAc) ₂ catalyst and Pd(1,3-bisdiphenylphosphinopropane)(OAc) ₂ One or more of the group consisting of catalysts.

13. The catalyst composition for preparing a polyketone compound according to claim 1, characterized in that it comprises a carrier surface-modified with a sulfonic acid group or an onium salt compound of a carboxylic acid group and the catalyst composition of the palladium-based catalyst. The equivalence ratio is 1:0.1 to 1:10.

14. A palladium mixed catalyst system for preparing polyketone compounds, characterized by comprising the catalyst composition for preparing polyketone compounds according to claim 1, using olefin and carbon monoxide as reactants.

15. A method for preparing polyketone, comprising:

The step of dispersing the catalyst composition for preparing a polyketone compound according to claim 1 in a solvent; and

The step of adding olefin and carbon monoxide to the dispersed said catalyst composition to carry out the polymerization.

16. The method for preparing polyketone according to claim 15, wherein the solvent is an alcohol compound having 1 to 20 carbon atoms.

17 . The method for preparing polyketone according to claim 15 , wherein the carrier or carboxylic acid comprising surface modification with a sulfonic acid group is added at a molar concentration of 0.1×10 ⁻³ M to 1.0×10 ⁻³ M. 18 . base onium salt compounds.

18. The method for preparing polyketone according to claim 15, wherein the catalyst composition for preparing a polyketone compound comprises a carrier whose surface is modified with a sulfonic acid group, and the surface is modified with a sulfonic acid group. Modified supports are prepared by adding sulfuric acid or chlorosulfonic acid to the support.

19 . The method for preparing polyketone according to claim 15 , wherein the palladium-based catalyst is contained in a molar concentration of 0.1×10 ⁻³ M to 1.0×10 ⁻³ M. 20 .

20. The method for preparing polyketone according to claim 15, wherein the olefin is ethylene, propylene, hexene, decene or a mixture thereof.

21. The method for preparing polyketone according to claim 15, wherein the olefin and the carbon monoxide are added in a ratio of 20-30 bar:30-40 bar.

22. The method for preparing polyketone according to claim 15, wherein the polymerization is performed at 50°C to 150°C.

23. The method for preparing polyketone according to claim 15, wherein the method for preparing polyketone is a method without adding seeds.

24. A polyketone polymer, characterized in that it is formed by the method for preparing polyketone according to claim 15, and has an apparent density of 0.1 to 0.5 g/ml.