WO2012173413A2 - Carbon monoxide/olefin copolymerizing catalyst and suspension polymerization using same - Google Patents

Abstract

The present invention relates to a carbon monoxide/olefin copolymerizing catalyst, and to a suspension-polymerization production process using same. More particularly, the present invention relates to a compound expressed by chemical formula 1 and comprising an alkyl having a hydrophobic group or an aryl sulfonate anion (RSO₃ ^-), to a carbon monoxide/olefin copolymerizing catalyst using the compound, and to a method for preparing polyketones using the catalyst. When using the catalyst, a carbon monoxide/olefin suspension polymerization can be achieved, and polymer particles can be produced having a high bulk density and in which the shape of the particles can be adjusted to be spherical or granular, thus enabling easy mass production.

Description

Carbon monoxide / olefin copolymer catalyst and suspension polymerization using the same

The present invention relates to a carbon monoxide / olefin copolymer catalyst and a suspension polymerization production process using the catalyst.

Carbon monoxide / olefin copolymers, also known as polyketones, can be used as raw materials for high strength fibers and engineering plastics (Chem. Rev. 1996, 96, 663). The first catalyst for this polymerization was published by Reppe in the 1940's (US Pat. No. 2,577,208 (1951)). When K ₂ Ni (CN) ₄ was used as a catalyst to react ethylene and carbon monoxide in water, a low molecular weight oligomer was obtained with a dispersion of diethyl ketone and propionic acid. Later, commercially available high activity catalysts were developed by Shell in the 1980s (European Patent No. 121,965 (1984); J. Organomet. Chem. 1991, 417, 235). The high activity catalyst claimed by the Shell company is a compound comprising two non-coordinating anions of palladium divalent coordinated by a bidentate phosphine ligand, as shown in Structural Formula 1 below. Typically, in the following structural formula 1, M is a person group, a bridge R is-[C (R ⁵ R ⁶ )] _3- , R ¹ to R ⁴ is a catalyst showing high activity when aryl. In particular the following structural formula 2, 3-bis [di (o - methoxyphenyl) phosphino] propane {1,3-bis [di (o -methoxyphenyl) phosphino] propane} ligand is coordinated to the palladium catalyst is only in the active surface It is known to show high performance in terms of molecular weight (European Patent No. 257,663 (1988)). After Structure 3 of 1,3-bis [di (o - methoxyphenyl) phosphino] propane-2-sila {1,3-bis [di (o -methoxyphenyl) phosphino] -2-silapropane} a ligand is coordinated to A carbon monoxide / ethylene copolymerization reaction using a palladium compound has been disclosed (US Pat. No. 4,994,592 (1991)). In the following Structural Formula 1 , the non-coordinating anion Y ⁻ is a conjugate anion of an acid having a PKa value of 2 or less, and in general, in consideration of economical efficiency and activity, a paratolulensulfonate anion or a trifluoroacetate anion is used.

Carbon monoxide / olefin copolymerization reactions have not yet been commercialized in large quantities, despite active research and development. This is due to the inability to control the shape of the obtained polymer particles and the development of a continuous production process. The carbon monoxide / ethylene copolymer has a very low solubility in conventional organic solvents, resulting in a precipitate composed of amorphous white snow particles during the polymerization reaction, which causes problems such as transport for post-treatment, making it difficult to produce continuous processes. . In addition, when a precipitate composed of such amorphous snow particles is obtained, the bulk density is low, resulting in a low productivity per unit reactor volume.

Particle shape control is very important when preparing polymers. The method for producing spherical polymer particles using the suspension polymerization method in the radical polymerization reaction is very useful commercially by the conventional method. In the production of polyethylene or polypropylene through coordination polymerization with Ziegler-Natta catalysts, the shape of the resulting polymer particles must be controlled to enable continuous production through slurry or gas phase processes. In this case, the particle shape is usually controlled by supporting a catalyst on silica or MgCl ₂ (Korean Patent No. 354,290; Macromolecues 2000 , 33 , 3194-3195; Chem. Rev. 2000, 100, 1377-1390; Chem. Rev. 2000, 100, 1347-1376).

Thus, the present inventors is CF ₃ SO ₃ being studied in order to overcome the problems of the prior art, efforts result, commonly used ^- (OTf _{anion), CH 3 C 6 H 4} SO 3 - (OTs anion) or CF ₃ Palladium compounds with CO ₂ ^- anions show no activity in carbon monoxide / olefin copolymerization reactions in nonpolar organic solvents such as 1-octanol, but alkyl or aryl with hydrophobic groups such as dodecylbenzenesulfonate Palladium compounds with sulfonate anions (RSO ₃ ⁻ ) are found to be active in carbon monoxide / olefin copolymerization reactions in nonpolar organic solvents that do not mix with water such as 1-octanol. When dissolved in a non-polar organic solvent that is not mixed with water and dispersed in water to implement carbon monoxide / olefin suspension polymerization, the particle shape is spherical or granular. By ensuring that there can be prepared a section of high polymer particle bulk condenser T, thereby completing the present invention.

Accordingly, the present invention is to provide a palladium compound having an alkyl or aryl sulfonate anion (RSO ₃ ⁻ ) as a non-coordinating anion.

It is another object of the present invention to provide a catalyst for carbon monoxide / olefin copolymerization.

In another aspect, the present invention is to provide a method for producing a polyketone using the catalyst as a third object.

Finally, the present invention is to provide a polyketone produced by the above production method as a fourth problem.

In order to achieve the first object of the present invention,

It provides a compound represented by the following formula (1):

[Formula 1]

In Chemical Formula 1,

R is (C6-C20) alkyl or (C6-C20) alkyl (C6-C20) aryl;

n is an integer of 1 or 2;

A is (C1-C20) alkyl or (C1-C20) acyl;

Z is carbon or silicon;

R ¹ and R ² are each independently (C ¹ -C 20) alkyl; (C1-C20) alkyl comprising at least one selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl comprising at least one selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl including one or more selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl comprising at least one selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkoxy; Or (C6-C30) aryloxy; R ¹ and R ² may be linked to each other to form a ring;

Each R ³ is independently (C 1 -C 20) alkyl;

R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently hydrogen; halogen; (C1-C20) alkyl; (C1-C20) alkyl comprising at least one selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl comprising at least one selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl including one or more selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl comprising at least one selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkoxy; (C6-C30) aryloxy; Formyl; (C1-C20) alkylcarbonyl; (C6-C20) arylcarbonyl; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl; Two or more of R ⁴ , R ⁵ , R ^6, and R ⁷ may be connected to each other to form a ring.

In order to achieve the second object of the present invention,

It provides a catalyst for carbon monoxide / olefin copolymerization represented by the formula (1).

In order to achieve the third object of the present invention,

Provided is a method for preparing a polyketone by dissolving the compound represented by Formula 1 in an organic solvent to disperse the solution in water to copolymerize carbon monoxide and olefins having 2 to 20 carbon atoms.

In order to achieve the fourth object of the present invention,

It is prepared by the above production method is composed of spherical or granular polymer particles having a particle diameter of 0.02 ~ 2 mm, to provide a polyketone having a bulk density of 0.20 ~ 0.30 g / mL.

The present invention is characterized in that the carbon monoxide / olefin copolymerization reaction is implemented by the suspension polymerization method. In the case of implementing suspension polymerization using the compound according to the present invention, it is possible to obtain polymer particles in which the particle shape is controlled to be spherical or granular, and to prepare polymer particles having a high bulk density, thereby facilitating mass production. .

1 is a photograph showing the shape of the polyketone particles prepared according to Example 7 (stirring speed 800 rpm).

2 is a photograph showing an example of polyketone particle size control according to Example 7.

Figure 3 is a photograph showing an example of polyketone particle size control by the suspension stabilizer concentration change according to Example 8.

Figure 4 is a photograph showing the particle shape of the polyketone prepared using the catalyst of Example 2 (a = 15), without adding a suspension stabilizer.

The present invention relates to a carbon monoxide / olefin copolymer catalyst and a process for producing polyketone by suspension polymerization using the catalyst.

The present invention will be described in more detail as follows.

The present invention provides a compound represented by Formula 1:

[Formula 1]

In Chemical Formula 1,

R is (C6-C20) alkyl or (C6-C20) alkyl (C6-C20) aryl;

n is an integer of 1 or 2;

A is (C1-C20) alkyl or (C1-C20) acyl;

Z is carbon or silicon;

R ¹ and R ² are each independently (C ¹ -C 20) alkyl; (C1-C20) alkyl comprising at least one selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl comprising at least one selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl including one or more selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl comprising at least one selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkoxy; Or (C6-C30) aryloxy; R ¹ and R ² may be linked to each other to form a ring;

Each R ³ is independently (C 1 -C 20) alkyl;

R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently hydrogen; halogen; (C1-C20) alkyl; (C1-C20) alkyl comprising at least one selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl comprising at least one selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl including one or more selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl comprising at least one selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkoxy; (C6-C30) aryloxy; Formyl; (C1-C20) alkylcarbonyl; (C6-C20) arylcarbonyl; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl; Two or more of R ⁴ , R ⁵ , R ^6, and R ⁷ may be connected to each other to form a ring.

In the present invention, the compound represented by Chemical Formula 1 may be used as a catalyst for carbon monoxide / olefin copolymerization.

One of the features of the compound represented by Formula 1 is that R includes a RSO ₃ ⁻ anion wherein (C6-C20) alkyl or (C6-C20) alkyl (C6-C20) aryl.

Palladium compounds containing RSO ₃ ^- anion wherein R is (C6-C20) alkyl or (C6-C20) alkyl (C6-C20) aryl according to the invention show polymerization activity in a nonpolar organic solvent that is not mixed with water. It is possible to implement suspension polymerization, another feature of the invention. An example of carbon monoxide / olefin copolymerization using the palladium compound containing the characteristic anion of the present invention as a catalyst has not been reported. Published documents or patents commonly catalyze palladium compounds comprising CF ₃ SO ₃ ⁻ (OTf anion), CH ₃ C ₆ H ₄ SO ₃ ⁻ (OTs anion), CF ₃ CO ₂ ⁻ or BF ₄ ⁻ as an anion. Carbon monoxide / olefin copolymerization was carried out (Chemical Review 96 (1996), 663; European Patent 257663 (1987); European Patent 121965 (1989); European Patent 222454 (1993); Jornal or Organometallic Chemstry 417 (1991), 235). The are commonly used on CF ₃ SO ₃ ^- (OTf _{anion), CH 3 C 6 H 4} SO 3 - (OTs negative ion), CF ₃ CO ₂ ^- or BF ₄ ^- palladium catalyst containing an anion is 1-octanol It does not show polymerization activity in nonpolar organic solvents that do not mix with water such as (see Comparative Example).

The compound represented by Formula 1, wherein n is 2, can be prepared by, for example, reacting 2 equivalents of RSO ₃ H with a Pd (OAc) ₂ compound coordinated with a bidentate bisphosphine ligand. The compound of n is 1 prepared by reacting 1 equivalent of RSO ₃ Ag or RSO ₃ Na with a ligand-coordinated Pd (A) Cl compound, wherein A is (C1-C20) alkyl or (C1-C20) acyl can do. Such metallization methods are already known by many researchers. In addition to the metallization method, a compound of the present invention may be prepared using a method known in the art without limitation. The compound of n is 1 is known as a species that is generated by the compound of n is activated under the copolymerization reaction conditions.

More preferably in the compound represented by Formula 1, R is dodecylbenzene (C ₁₂ H ₂₅ C ₆ H _4- ); n is preferably 2. Dodecylbenzenesulfonic acid (C ₁₂ H ₂₅ C ₆ H ₄ SO ₃ H) is a compound that is commercially produced and used in large quantities in RSO ₃ H has the advantage of easy access, low cost. A compound of n is easily prepared by reacting 2 equivalents of dodecylbenzenesulfonic acid (C ₁₂ H ₂₅ C ₆ H ₄ SO ₃ H) with a Pd (OAc) ₂ compound coordinated with a bisphosphine ligand.

Most preferably, in Formula 1, R is dodecylbenzene (C ₁₂ H ₂₅ C ₆ H _4- ); n is 2; Z is silicon; R ² and R ³ are methyl; R ⁴ to R ⁷ are hydrogen; R ¹ is preferably -CH ₂ [CH ₂ ] _a CH ₃ , where a is an integer from 9 to 18.

Bisphosphine ligand of the compound represented by the formula (1) of the present invention can be prepared by the following scheme 1 devised by the present inventors as a novel compound.

[Scheme 1]

The addition of diethylamine to the compound of formula 6 converts it quantitatively into the compound of formula 7 (J. Am. Chem. Soc. 1990, 112, 5244-5252). The compound of formula 7 is oxidized in air, so that the purification process is not easy. However, the compound of formula 6 is stable in air and is easy to purify by conventional organic compound purification methods such as chromatography. By reacting an organolithium compound of formula 4 with dichloro xylene compound of formula 5 it can be synthesized in high yield the compound of formula 6. The reaction for forming new silicon-carbon bonds by chlorosilane nucleophilic attack of the organolithium compound is a known reaction and has a high yield. The dichlorosilane compound of formula 5 is readily prepared by the hydrosilylation reaction of alkenes. The hydrosilylation reaction is a commercially useful reaction in which a H ₂ PtCl ₆ compound is generally used as a high activity catalyst (eg, Org. Lett, 1999, vol. 1, # 12 p. 1925 ~ 1927). Starting materials, alkenes and dichloromethylsilane compounds are those that are readily available on the market or that can be easily synthesized. The organolithium compound of formula 4 may be prepared by adding BH ₃ to a di (2-methoxyphenyl) methylphosphine compound, followed by butyllithium (eg J. Am. Chem. Soc. 1990, 112, 5244-5252). Di (2-methoxyphenyl) methylphosphine [Di (2-methoxyphenyl) methylphosphine] can be synthesized with reference to known literature (Phosphorus and sulfur, 1985, vol. 24, p259-271).

As described above in the background, US Patent No. 4,994,592 discloses the synthesis of 1,3-bis [di ( o -methoxyphenyl) phosphino] -2-silapropane ligand of Structural Formula 3 , from which Synthesis of general bisphosphine ligands of formula 9 is disclosed. However, the 4,994,592 of U.S. Patent R 'is according to formula No. 7 compound with the structure is different, the United States registered in Patent 4994592 in the scheme 1, the invention here is limited to hydrocarbyl having a carbon number of 10 or less Structure 9 The ligand of is prepared by the following Scheme 2. The compound of formula 8 , which is required to synthesize the compound of formula 9 , can be purchased commercially only the compound in which both R's are methyl, other derivatives are not available, and the synthesis is not easy. There is a problem. In particular, ((CH ₃ (CH ₂ ) _a CH ₂ CH ₂ ) (Me) Si (CH ₂ Cl) which is _a reagent required for synthesizing the compound of Formula 7 of the present invention by the method disclosed in US Pat. No. 4,994,592 ) ₂ is not a known compound and is not easy to synthesize by the method disclosed in US Patent No. 4,994,592.

Scheme 2

In another embodiment of the present invention, there is provided a method of preparing polyketone particles by copolymerizing carbon monoxide and olefins having 2 to 20 carbon atoms by dispersing a solution of the compound represented by Formula 1 in an organic solvent in water.

The present invention is characterized by implementing the carbon monoxide / olefin copolymerization reaction by suspension polymerization method. By implementing suspension polymerization, polymers in the form of finely controlled particles can be obtained, which are suitable for mass production and increase the bulk density of the particles to improve productivity.

The compound represented by Chemical Formula 1 of the present invention may implement suspension polymerization by having solubility and activity in an organic solvent which is not mixed with water as described above.

Typically is used on CF ₃ SO ₃ ^- (OTf _{anion), CH 3 C 6 H 4} SO 3 - (OTs negative ion), CF ₃ CO ₂ ^- or BF ₄ ^- palladium compound containing silver mixed with water, such as methanol In the polar protic solvent, as shown in the comparative example, as shown in the comparative example, a non-polar organic solvent which is not mixed with water such as 1-octanol does not show the polymerization activity and has a disadvantage in that suspension polymerization cannot be realized. Typically the carbon monoxide / olefin copolymerization reaction is carried out in methanol. An example of performing a carbon monoxide / olefin copolymerization reaction in a water solvent using a palladium compound prepared from a hydrophilic ligand has been reported. Further examples of performing a carbon monoxide / olefin copolymerization reaction in a non-polar organic solvent and water immiscible, such as toluene was reported by BASF Corporation The bidentate ratio Al a Pd (OAc) ₂ compound coordinated to the bisphosphine ligand Rommie Noksan cocatalyst Activated catalyst system (European Patent 590942 (1992)). Alomioxane compounds are highly reactive compounds that react violently with water and oxygen and cannot implement suspension polymerization, which is a characteristic of this reaction. The compound represented by Formula 1 according to the present invention contains a sulfonate anion of a hydrophobic (C6-C20) alkyl or a (C6-C20) alkyl (C6-C20) aryl group, and is not mixed with water. Suspension polymerization can be realized by showing polymerization activity in a solvent.

An organic solvent which is not mixed with water means that the solubility in water is less than 3%, an alcohol compound having 6 to 20 carbon atoms, a ketone compound having 6 to 20 carbon atoms, an ester compound having 6 to 20 carbon atoms, and an ether compound having 5 to 20 carbon atoms , A haloalkene compound having 1 to 10 carbon atoms, a haloarene compound having 6 to 20 carbon atoms, or the like can be used as a solvent. More specifically, hexanol, heptanol, octanol, 2-ethyl-1-octanol, decanol, dodecanol, hexanone, butyl acetate, methyl tert-butyl ether, dibutyl ether, methylene chloride, chloroform, Chlorobenzene may be used, and the solvent may be used alone or in combination of two or more thereof.

In the present invention, a solution in which the compound represented by Chemical Formula 1 is dissolved in an organic solvent is dispersed in water, wherein the water may include a suspension stabilizer. The suspension stabilizer may be used without limitation in the general suspension polymerization, for example, polyvinylpyrrolidone (PVP), poly [(vinyl alcohol) -co- (vinylacetate)] {poly [( vinyl alcohol) -co- (vinyl acetate)]}, natural gums, cellulose ethers, cellulose esters, and the like. The suspension stabilizers may be used alone or in combination of two or more thereof. As the poly [(vinyl alcohol) -co- (vinylacetate)], it is preferable to use 85 to 92% partial hydrolysis of poly (vinyl acetate) [poly (vinyl acetate)]. In addition to the suspension stabilizer described above, synthetic organic polymers (trade name, Span Tween, etc.) dissolved in water may also be used as the suspension stabilizer. The present invention can implement suspension polymerization without a suspension stabilizer, but in order to prepare the particles of the resulting polymer into a uniform spherical or granular form, it is more preferable to add a suspension stabilizer to polymerize. The suspension stabilizer is preferably used by dissolving in water, and the amount used is not limited, but more preferably, it is preferably used by dissolving the suspension stabilizer 0.01 to 1.0 mass% relative to the mass of water. It can control the size of the polymer particles produced through.

The volume ratio of the water and the organic solvent used in the method for producing the polyketone particles is preferably in the range of 1: 0.01 to 1.0, more preferably 1: 0.1 to 0.5 range.

Specific examples of the olefin compound used in the polymerization reaction include ethylene, propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, cyclopentene, norbornene , Dicyclopentadiene, cyclooctene, cyclododecene, styrene, alphaketylstyrene, acrylic acid and alkyl esters thereof, methacrylic acid and alkyl esters thereof, and the like. Can be used in combination.

The molar ratio of carbon monoxide and olefin is preferably in the range of 95: 5 to 5:95, more preferably 5: 1 to 1: 5. Reaction temperature is 10^oC to 200^oC, more preferably 40^oC-100^oMaintain a C range. Since carbon monoxide and some olefins are gases at this temperature, the polymerization reaction is usually carried out in a pressure reactor, and the pressure inside the reactor is usually 200 atm or less, more preferably 100 atm or less. A typical suspension polymerization method is Colloid. Polym. Sci. 270: 717-732 (1992), and the like, which can be easily carried out with reference to this.

In the above production method, preferably, the organic solvent is an alcohol compound having 6 to 20 carbon atoms; In Formula 1, R is dodecylbenzene (C ₁₂ H ₂₅ C ₆ H _4- ), and n is preferably used as a catalyst compound. Dodecylbenzenesulfonic acid (C ₁₂ H ₂₅ C ₆ H ₄ SO ₃ H) is a compound that is commercially produced and used in large quantities has the advantage of easy access, low cost. A compound of n is easily prepared by reacting 2 equivalents of dodecylbenzenesulfonic acid (C ₁₂ H ₂₅ C ₆ H ₄ SO ₃ H) with a Pd (OAc) ₂ compound coordinated with a bisphosphine ligand.

More preferably the organic solvent is an alcohol compound having 6 to 20 carbon atoms; R is dodecylbenzene (C ₁₂ H ₂₅ C ₆ H _4- ); n is 2; Z is silicon; R ² and R ³ are methyl; R ⁴ to R ⁷ are hydrogen; R ¹ is preferably -CH ₂ [CH ₂ ] _a CH ₃ , wherein a is an integer from 9 to 18, and most preferably the organic solvent is 1-octanol; The suspension stabilizer is poly [(vinyl alcohol) -co- (vinylacetate)]; The olefin is ethylene, propylene or mixtures thereof; R is dodecylbenzene (C ₁₂ H ₂₅ C ₆ H _4- ); n is 2; Z is silicon; R ² and R ³ are methyl; R ⁴ to R ⁷ are hydrogen; R ¹ is —CH ₂ [CH ₂ ] _a CH ₃ wherein a is an integer of 9 to 18. The 1-octanol is an alcohol compound that is not mixed with water at all and is manufactured in large quantities in the industry, and the unit price is low. As the suspension stabilizer, poly [(vinyl alcohol) -co- (vinylacetate)] prepared by partially hydrolyzing poly (vinylacetate) by 87 to 89% is more effective. The palladium compound used as a catalyst for the carbon monoxide / olefin copolymer is an ionic compound, and a polar protic solvent such as methanol is usually the most preferable solvent, but methanol cannot be suspended because of mixing with water. Most preferably, the palladium compound is dissolved in an alcohol compound which is not mixed with water to implement polymerization on the alcohol to implement suspension polymerization. At this time, the alcohol compound having 5 or less carbon atoms is mixed with water, but the alcohol compound having 6 or more carbon atoms is not mixed with water, so to implement suspension polymerization, it is preferable to use an alcohol compound having 6 or more carbon atoms. The solubility of water at 20 degrees Celsius of 1-hexanol is known as 0.6%.

In another aspect, the present invention is prepared according to the manufacturing method, a bulk ketone precipitate consisting of granular or spherical polymer particles having a particle diameter of 0.02 to 2 mm ranges from 0.20 g / mL to 0.30 g / mL. to provide. Polyketone precipitates with a bulk density of at least 0.20 g / mL have been reported so far.

Hereinafter, the present invention will be described in detail in the following Examples, but the protection scope of the present invention is not limited only to the following Examples.

Preparation Example Synthesis of Compound of Structural Formula 5 (a = 5, 9, 15)

1-octene, 1-dodecene, and 1-octadecene were synthesized using conventional experimental methods using Speier catalyst, respectively. 1-octene (2.00 g, 17.8 mmol) tetrahydrofuran (20 mL) solution of methyl dichloro silane dissolved in a (3.07 g, 26.7 mmol) and Speier catalyst _{(H 2 PtCl 6 · H 2} O to iso- propanol To 10% (w / w) dissolved in a solution, 200 ppm) was added. Stir at room temperature for 1 hour and overnight at 80 ^° C. After the reaction was completed, the remaining solvent and dichloromethylsilane were removed using a vacuum line. As a result of analyzing the NMR data of the obtained compound, it was used in the next reaction without further purification. 1-dodecene and 1-octadecene were also tested using the above conditions and experimental methods. The obtained compounds also confirmed that the reaction quantitatively by analyzing the NMR data.

Example 1 Ligand Synthesis of Structural Formula 7 (a = 5, 9, 15)

(2-MeOPh) ₂ MeP was synthesized by methods known in the literature (Phosphorus and sulfur, 1985, vol. 24, p259-271). (2-MeOPh) ₂ MeP.BH ₃ was prepared by the following method. A solution of (CH ₃ ) ₂ S.BH ₃ (0.35 g, 4.61 mmol) diluted in 1 mL of toluene was injected into a solution of (2-MeOPh) ₂ MeP (1.00 g, 3.84 mmol) in 15 mL of toluene. After stirring overnight at room temperature, the remaining solvent was removed. Purification of the compound by silica gel column chromatography using toluene yielded 800 mg of the compound (yield 76%). ¹ H NMR (CDCl ₃ ): 7.60 (q, J = 7.2 Hz, 2H, CH), 7.47-7.38 (m, 2H, CH), 7.04-6.94 (m, 2H, CH), 6.88 (q, J = 4, 2H, CH) 3.69 (s, 6H, OCH ₃ ), 1.97 (d, J = 11.2, CH ₃ ) ppm. ¹³ C { ¹ H} NMR (100 MHz, CDCl ₃ , 298 K): δ 160.87, 133.85, 133.74, 132.57, 132.55, 120.57, 120.47, 118.40, 117.82, 111.20, 111.15, 55.47, 11.30, 10.87 ppm.

The Schlenk flask containing the resulting (2-MeOPh) ₂ MeP.BH ₃ (1.00 g, 3.65 mmol) and tetrahydrofuran (6 mL) was immersed in a -78 ^° C. cold bath, lowered in temperature, and stirred under sec-butyl under stirring. Lithium (1.18 mL, 3.65 mmol, 1.4 M cyclohexane solution) was slowly injected. After stirring for 2 hours at low temperature, a solution of (CH ₃ (CH ₂ ) ₇ ) (CH ₃ ) SiCl ₂ (0.506 g, 1.82 mmol) (a = 5) diluted in tetrahydrofuran (2 mL) was slowly injected. It was. After stirring at −78 ^° C. for 1 hour, the temperature was slowly raised to room temperature. After stirring at room temperature for 3 hours, an aqueous solution of ammonium chloride (10 mL) was added thereto to terminate the reaction. The solution was transferred to a separatory funnel to extract the organic layer. The organic layer was taken, the moisture was removed with anhydrous magnesium sulfate, and the solvent was removed to obtain a solid material. The compound was purified by silica gel column chromatography using a mixed solvent of hexane and ethyl acetate (v / v, 20: 1) to obtain 1.05 g of a compound (yield 82%). ¹ H NMR (C ₆ D ₆ ): 8.00-7.82 (m, 4H, CH), 7.14-7.04 (m, 4H, CH), 6.86-6.70 (m, 4H, CH), 3.22 (s, 6H, OCH ₃ ), 3.19 (s, 6H, OCH ₃ ), 2.55-2.25 (m, 4H, SiCH ₂ ), 1.40-1.15 (m, 12H, CH ₂ ), 0.92 (t, J = 6.8, 3H, CH ₃ ) , 0.85-0.70 (m, 2H, CH ₂ Si), 0.00 (s, 3H, CH3) ppm.

Diethylamine (1.00 mL, 9.67 mmol) was added to a solution of the obtained compound of formula 6 (1.00 g, 1.42 mmol) in toluene (2 mL), and the mixture was stirred at 55 ^° C. for 1 day. Toluene and diethylamine remaining after completion of the reaction were removed using a vacuum line. Under a nitrogen atmosphere, the compound was purified by alumina column chromatography using a mixed solution of hexane and diethyl ether (v / v, 1: 1) to obtain 690 mg of a compound (yield 72%). ¹ H NMR (C ₆ D ₆ ): 3.30 (s, 6H, OCH ₃ ), 3.29 (s, 6H, OCH ₃ ), 1.80-1.60 (m, 4H, SiCH ₂ ), 1.50-1.20 (m, 12H, CH ₂ ), 0.97 (t, J = 6.8, 3H, CH ₃ ), 0.85-0.70 (m, 2H, SiCH ₂ ), 0.15 (s, 3H, CH ₃ ) ppm.

Ligand of structure 7 having a = 9 was synthesized using (CH ₃ (CH ₂ ) ₁₁ ) (CH ₃ ) SiCl ₂ using the above conditions and experimental methods. The compound was purified by silica gel column chromatography using a mixed solvent of hexane and ethyl acetate (v / v, 20: 1) to obtain 980 mg of a compound (yield 70%). ¹ H NMR (C ₆ D ₆ ): 3.22 (s, 6H, OCH ₃ ), 3.19 (s, 6H, OCH ₃ ), 2.55-2.25 (m, 4H, CH ₂ ), 1.40-1.15 (m, H, CH ₂ ), 0.92 (t, J = 6.8 3H, CH ₃ ), 0.85-0.75 (m, 2H, CH ₂ Si), 0.01 (s, 3H, CH ₃ ) ppm. In order to remove BH ₃ of the obtained compound, it was synthesized using diethylamine using the above conditions and experimental method. Under a nitrogen atmosphere, the compound was purified by alumina column chromatography using a mixed solution of hexane and diethyl ether (v / v, 1: 1) to obtain 625 mg of a compound (yield 65%). ¹ H NMR (C ₆ D ₆ ): 3.26 (s, 6H, OCH ₃ ), 3.24 (s, 6H, OCH ₃ ), 1.74-1.60 (m, 4H, SiCH ₂ ), 1.40-1.20 (m, 20H, CH ₂ ), 0.92 (t, J = 6.8, 3H, CH ₃ ), 0.80-0.70 (m, 2H, CH ₂ Si), 0.13 (s, 3H, CH ₃ ) ppm.

Ligand of structure 7 having a = 15 was synthesized using (CH ₃ (CH ₂ ) ₁₇ ) (CH ₃ ) SiCl ₂ using the above conditions and experimental methods. The compound was purified by silica gel column chromatography using a mixed solvent of hexane and ethyl acetate (v / v, 20: 1) to obtain 1.06 g of a compound (yield 69%). ¹ H NMR (C ₆ D ₆ ): 3.26 (s, 6H, OCH ₃ ), 3.24 (s, 6H, OCH ₃ ), 1.74-1.60 (m, 4H, SiCH ₂ ), 1.40-1.20 (m, 20H, CH ₂ ), 0.92 (t, J = 6.8, 3H, CH ₃ ), 0.80-0.70 (m, 2H, CH ₂ Si), 0.13 (s, 3H, CH ₃ ) ppm. In order to remove BH ₃ of the obtained compound, it was synthesized using diethylamine using the above conditions and experimental method. Under a nitrogen atmosphere, the compound was purified by alumina column chromatography using a mixed solution of hexane and diethyl ether (v / v, 1: 1) to obtain 677 mg of a compound (yield 70%). ¹ H NMR (C ₆ D ₆ ): 3.65 (s, 6H, OCH ₃ ), 3.64 (s, 6H, OCH ₃ ), 2.08-1.90 (m, 4H, SiCH ₂ ), 1.40-1.10 (m, 35H, CH ₂ ), 0.42-0.32 (m, 2H, CH ₂ Si), -0.36 (s, 3H, CH ₃ ) ppm.

Example 2 Catalyst Synthesis of Structural Formula 10

(CH ₃ CN) ₂ PdCl ₂ (0.10 g, 0.39 mmol) in dichloromethane (10 mL) in a solution of the formula 7 synthesized in Example 1 (a = 5, 0.26 g, 0.39 mmol) Was dissolved in dichloromethane (1 mL). After stirring at room temperature for 5 hours, the remaining solvent was removed. The yellow solid obtained by-product was removed using diethyl ether (2 mL). The remaining solvent was removed to give a compound (300 mg) as a yellow powder (yield 92%). Silver acetate (39.2 mg, 0.23 mmol) was added to a solution of the obtained compound (0.10 g, 0.12 mmol) in methanol (4 mL). Stirred overnight at room temperature with light blocked. After the solvent was removed, the resultant was dissolved in dichloromethane (3 mL) and filtered to remove silver chloride. After the solvent was removed, byproducts were removed with diethyl ether, and the remaining solvent was removed to obtain a yellow powder catalyst (100 mg) (yield 95%). ¹ H NMR (400 MHz, CD ₃ OD): δ 8.00-7.40 (b, 4H, CH), 7.40-7.00 (b, 12H, CH), 4.40-3.60 (b, 12H, OCH ₃ ), 2.20-1.80 (b, 6H, O (CO) CH ₃ ), 1.50-0.95 (m, H, SiCH ₂ , CH ₂ ), 0.91 (t, 3H, J = 7.2, CH ₃ ), -0.06 (t, 2H, J = 6.8, CH ₂ Si), -0.42 (s, 3H, SiCH ₃ ) ppm. The solution obtained by dissolving the obtained compound (0.10 g, 0.11 mmol) in methanol (3 mL) was cooled to -30 ^o C, and then the solution of dodecylbenzenesulfonic acid (72.6 mg, 0.22 mmol) in methanol (1 mL) was dissolved. Inject. Stir overnight at room temperature. The remaining solvent was removed, by-products were removed with hexane, and the solvent was removed to obtain 150 mg of a yellow powder compound (a = 5) (yield 92%). ¹ H NMR (400 MHz, CD ₃ OD): δ7.90-7.70 (b, 4H, CH), 7.67 (d, J = 8.4, 4H, CH), 7.40-7.10 (m, 12H, CH), 7.20 (dd, J = 8.4, 4H, CH), 4.04 (s, 12H, OCH ₃ ), 2.20-1.90 (b, 4H, SiCH 2), 1.80-0.80 (m, 62H, CH ₂ ), 0.77 (t, 3H , J = 7.6, CH ₃ ), 0.04 (t, 2H, J = 7.6, CH ₂ Si), -0.30 (s, 3H, SiCH ₃ ) ppm.

100 mg (yield 95%) of a yellow powder of the acetate compound was obtained under the conditions and the experimental method using the ligand of Structural Formula 7 having a = 9. ¹ H NMR (400 MHz, CD ₃ OD): δ7.90-7.50 (b, 4H, CH), 7.40-7.00 (b, 12H, CH), 4.20-3.70 (b, 12H, OCH ₃ ), 2.20- 1.80 (b, 6H, O (CO) CH ₃ ), 1.50-0.95 (m, 20H, SiCH ₂ , CH ₂ ), 0.91 (t, 3H, J = 6.8, CH ₃ ), -0.06 (t, 2H, J = 7.2, CH ₂ Si), -0.42 (s, 3H, SiCH ₃ ) ppm. 143 mg (yield 90%) of this compound (a = 9) of the yellow powder substituted by dodecylbenzenesulfonate by the said conditions and the experimental method was obtained. ¹ H NMR (400 MHz, CD ₃ OD): δ 7.81 (t, J = 6.8, 4H, CH), 7.67 (d, J = 5.6, 4H, CH), 7.45-7.10 (m, 12H, CH) , 7.20 (dd, J = 8.4, 4H, CH), 4.04 (s, 12H, OCH ₃ ), 2.20-1.90 (b, 4H, SiCH ₂ ), 1.80-0.80 (m, 70H, CH ₂ ), 0.77 ( t, 3H, J = 7.2, CH ₃ ), 0.04 (t, 2H, J = 6.0, CH ₂ Si), -0.30 (s, 3H, SiCH ₃ ) ppm.

100 mg (yield 95%) of a yellow powdered acetate compound was obtained under the conditions and the experimental method using the ligand of Structural Formula 7 having a = 15. ¹ H NMR (400 MHz, CD ₃ OD): δ 8.00-7.40 (b, 4H, CH), 7.40-7.00 (b, 12H, CH), 4.40-3.60 (b, 12H, OCH ₃ ), 2.20-1.80 (b, 6H, O (CO) CH ₃ ), 1.50-0.90 (m, 32H, SiCH ₂ , CH ₂ ), 0.85 (t, 3H, J = 6.8, CH ₃ ), -0.05-(-0.20) ( t, 2H, J = 6.8, CH ₂ Si), -0.49 (s, 3H, SiCH ₃ ) ppm. 142 mg (yield 92%) of compound (a = 15) as a yellow powder substituted with dodecylbenzenesulfonate was obtained under the above conditions and experimental methods. ¹ H NMR (400 MHz, CD ₃ OD): δ7.90-7.70 (b, 4H, CH), 7.63 (dd, J = 8.0, 4H, CH), 7.40-7.10 (m, 12H, CH), 7.19 (dd, J = 8.0, 4H, CH), 4.02 (s, 12H, OCH ₃ ), 2.20-1.90 (b, 4H, SiCH 2), 1.80-0.80 (m, 82H, CH ₂ ), 0.75 (t, 3H , J = 7.2, CH ₃ ), 0.01 (t, 2H, J = 7.6, CH ₂ Si), -0.33 (s, 3H, SiCH ₃ ) ppm.

Example 3 Catalyst Synthesis of Structural Formula 11 wherein Z of the Compound of Formula 1 is Carbon

(2-MeOPh) ₂ P (CH ₂ ) ₃ P (2-MeOPh) ₂ was synthesized by methods known in the literature (Eur. J. Inorga. Chem. 2005, p4794-4800, US Patent 4874897 (1989)). . Metallization reaction and anion substitution reaction were synthesized using the conditions and experimental method of Example 2. 164 mg of a yellow powder substituted with dodecylbenzenesulfonate was obtained using a compound substituted with acetate (0.1 g, 0.13 mmol) (yield 94%). ¹ H NMR (400 MHz, CD ₃ OD): δ7.65 (t, J = 7.2, 4H, CH), 7.60 (d, J = 8.0, 4H, CH), 7.40-7.25 (m, 4H, CH) , 7.30-7.20 (m, 4H, CH), 7.18 (dd, J = 8.0, 4H, CH), 7.00 (t, J = 7.2, 4H, CH), 4.03 (s, 12H, OCH ₃ ), 2.90- 2.70 (b, 4H, PCH ₂ ), 2.33-2.10 (b, 2H, CH ₂ ), 1.80-0.60 (m, 50H, J = 7.6, CH ₃ ), 0.04 (t, 2H, J = 7.6, CH ₂ Si), -0.30 (s, 3H, SiCH ₃ ) ppm.

[Example 4-6] In the formula 10 (a = 5, 9, 15), carbon monoxide / ethylene suspension polymerization reaction using a catalyst in which R is dodecylbenzene

After assembling the 100 ml bomb reactor in advance, the solution of each compound (0.005 mmol) prepared in Example 2 in 5 ml of 1-octanol and poly (vinylacetate) as a suspension stabilizer was 87 to 89%. 50 ml of an aqueous solution of 0.070 g of poly [(vinyl alcohol) -co- (vinylacetate)] prepared by partial hydrolysis was injected into the reactor through a syringe. Ethylene and carbon monoxide were added at a pressure of 70 bar at a ratio of 1: 1, and stirred at a speed of 700 rpm using an anchor type blade. The temperature was then raised to 85 ^° C. via a thermostat mounted on the reactor. As the reaction proceeded, it was possible to observe the pressure drop of the gas. After 1 hour and 30 minutes had elapsed after the temperature was applied, the reactor was cooled to room temperature and the reaction was terminated by removing the gas. The obtained polymer was filtered and then refluxed at 70 ^o C for 30 minutes using methanol, filtered to remove remaining 1-octanol, and solvent was removed for 2 hours in a vacuum oven at 90 ^o C. The activity of was calculated. Table 1 shows the activity and bulk density of the catalyst, Table 2 shows the size distribution of the obtained polymer. This was calculated from the mass ratio after separation using a standard sieve.

Example	mass (g)	activation (Kg / gPd · h)	shape	Bulkden City (g / ml)
4 (a = 5)	7.1	8.9	Granular	0.24
5 (a = 9)	7.1	8.9	Granular	0.25
6 (a = 15)	7.3	9.1	Granular	0.21

Example	mass (g)	2.0 ~ 1.0mm (wt%)	1.0mm ~ 850 μm (wt%)	850 ~ 710 μm (wt%)	710 ~ 600 μm (wt%)	600 ~ 500 μm (wt%)	500 ~ 425 μm (wt%)	425- 300 μm (wt%)	300 ~ 200 μm (wt%)	200 ~ 150 μm (wt%)	Average diameter (μm)
4	7.1	5.5	18.8	29.4	25.1	14.5	5.7	0.7	0.1	0	757
5	7.1	1.6	15.8	28.4	26.8	19.4	6.6	1.3	0.1	0	706
6	7.3	2.7	10.0	23.8	32.5	21.2	7.9	1.6	0.1	0	688

Example 7 Controlling Particle Size According to Stirring Rate in Carbon Monoxide / Ethylene Suspension Polymerization Using a Catalyst of Dodecylbenzene in Formula 10 (a = 15)

In the same manner as in Examples 4-6, the polymerization was carried out by adjusting the stirring speed to 500 to 800 rpm. As the stirring speed increases, the catalyst activity tends to increase gradually, and the average diameter of the particles decreases. The bulk density was 0.20 to 0.30 g / ml. Table 3 below shows the size distribution of the particles (FIGS. 1 and 2).

Stirring speed (r.p.m)	mass (g)	2.0 ~ 1.0mm (wt%)	1.0mm ~ 850 μm (wt%)	850 ~ 710 μm (wt%)	710 ~ 600 μm (wt%)	600 ~ 500 μm (wt%)	500 ~ 425 μm (wt%)	425- 300 μm (wt%)	300 ~ 200 μm (wt%)	200 ~ 150 μm (wt%)	Average diameter (μm)
500	5.3	16.1	80.9	2.4	0.6	0	0	0	0	0	1012
600	6.7	12.0	24.4	30.6	15.7	6.1	1.1	0.2	0	0	878
700	7.3	2.7	10.0	23.8	32.5	21.2	7.9	1.6	0.1	0	688
800	7.7	0.7	2.4	9.8	25.9	33.9	21.5	5.4	0.4	0	581

Through the above results, it can be seen that when using the catalyst of the present invention can adjust the size of the polyketone particles obtained only by controlling the stirring speed.

Example 8 Controlling Particle Size According to Suspension Stabilizer Concentration in Carbon Monoxide / Ethylene Suspension Polymerization Using a Catalyst of Dodecylbenzene in Structural Formula 10 (a = 15)

In the same manner as in Examples 4-6, the polymerization was carried out while changing the suspension stabilizer concentration from 0.07 to 0.56 wt%. As the suspension stabilizer increases, the catalytic activity tends to decrease gradually, and the average diameter of the particles decreases. The bulk density was 0.20 to 0.30 g / ml. In the absence of a suspension stabilizer, low bulk, partially granular particles were formed. Table 4 below shows the size distribution of the particles (FIGS. 3 and 4).

density (wt%)	mass (g)	2.0 ~ 1.0mm (wt%)	1.0mm ~ 850 μm (wt%)	850 ~ 710 μm (wt%)	710 ~ 600 μm (wt%)	600 ~ 500 μm (wt%)	500 ~ 425 μm (wt%)	425- 300 μm (wt%)	300 ~ 200 μm (wt%)	200 ~ 150 μm (wt%)	Average diameter (μm)
0.07	6.9	33.1	21.7	14.5	11.1	10.7	7.2	1.8	0.2	0	978
0.14	6.7	12.0	34.4	30.6	15.7	6.2	1.1	0.2	0.0	0	878
0.28	6.6	1.3	7.7	21.9	29.8	27.7	9.7	1.7	0.2	0	657
0.56	5.5	0	0.6	2.5	7.6	23.7	40.3	22.2	2.8	0.4	473

Through the above results, it can be seen that when using the catalyst of the present invention can adjust the shape and size of the polyketone particles obtained by adjusting the concentration of the suspension stabilizer.

Example 9-10 Carbon Monoxide / Ethylene Suspension Polymerization Reaction According to Ligand Structure of Catalyst

The catalyst was synthesized using the conditions and the experimental method of Example 2 using the ligand of Table 5, and the polymerization was carried out in the same manner as in Examples 4-6. The results are shown in Table 5 below. The stirring speed was 600 rpm and the suspension stabilizer concentration was 0.14 wt%.

Example	Ligand	mass (g)	activation (Kg / gPd · h)	shape	Bulkden City (g / ml)
9	1,3-bis [di ( o -methoxyphenyl) phosphino] propane	6.0	7.5	part Granular	0.12
10	1,3-bis [di ( o -methoxyphenyl) phosphino] -2-silapropane	6.6	8.3	part Granular	0.13

From the above results, even if the palladium catalyst does not have a large hydrophobic group in the bisphosphine ligand, but using RSO ₃ ⁻ having a high hydrophobic group as an anion, even if the bulk shape is not high because the particle shape is slightly irregular It was confirmed that the object of the present invention can be achieved by showing activity in the suspension polymerization reaction.

[Comparative Examples 1-5] Carbon Monoxide / Ethylene Suspension Polymerization Reaction According to the Change of Uncoordinated Anions

Synthesis of Catalysts with Various Uncoordinated Anions

Synthesis of the ^catalyst (Comparative Example 1) The non-coordinating anion ClO ₄

(CH ₃ CN) ₂ PdCl ₂ (0.10 g, 0.39 mmol) in dichloromethane (10 mL) was dissolved in dichloromethane (10 mL) to the ligand of formula 7 (a = 15) (0.31 g, 0.39 mmol) in dichloromethane ( 1 mL) was injected into the solution. After stirring at room temperature for 5 hours, the remaining solvent was removed. The yellow solid obtained by-product was removed using diethyl ether (2 mL). The remaining solvent was removed to give a yellow powder compound (360 mg) (yield 94%). Silver perchlorate (41.8 mg, 0.20 mmol) was added to a solution of the obtained compound (0.10 g, 0.10 mmol) in methanol (4 mL). Stirred overnight at room temperature with light blocked. After removing the solvent, it was dissolved in dichloromethane (3 mL) and filtered to remove silver chloride. After the solvent was removed, byproducts were removed with diethyl ether, and the remaining solvent was removed to obtain a catalyst (108 mg) as a yellow powder (yield 96%). ¹ H NMR (400 MHz, CD ₃ OD): δ 7.83 (t, J = 7.2, 4H, CH), 7.50-7.00 (m, 12H, CH), 4.04 (s, 12H, OCH ₃ ), 2.20- 1.90 (b, 4H, SiCH ₂ ), 1.50-1.00 (m, 32H, CH ₂ ), 0.91 (t, 3H, J = 6.8, CH ₃ ), 0.04 (t, 2H, J = 6.8, CH ₂ Si) , -0.28 (s, 3H, SiCH ₃ ) ppm.

(Comparative Example 2) A non-coordinating anion is _{CH 3 C 6 H 4 SO 3} - Synthesis of the catalysts

Silver paratoluenesulfonate (56.2 mg, 0.20 mmol) was used to obtain a yellow powder catalyst (120 mg) under the conditions and experimental method of Comparative Example 1 (yield 95%). ¹ H NMR (400 MHz, CD ₃ OD): δ8.00-7.70 (b, 4H, CH), 7.58 (d, J = 8, 4H, CH), 7.50-7.00 (b, 12H, CH), 7.19 (d, J = 8, 4H, CH), 4.02 (s, 12H, OCH 3), 2.36 (s, 6H, CCH ₃ ), 2.20-1.90 (b, 4H, SiCH ₂ ), 1.40-1.00 (m, 32H , CH ₂ ), 0.90 (t, 3H, J = 6.8, CH ₃ ), 0.01 (t, 2H, J = 7.6, CH ₂ Si), -0.32 (s, 3H, SiCH ₃ ) ppm.

(Comparative Example 3) The non-coordinating anion CF ₃ SO ₄ ^- Synthesis of the catalysts

Silver trifluoromethanesulfonate (55.0 mg, 0.20 mmol) was used as a yellow powder catalyst (118 mg) under the conditions and experimental method of Comparative Example 1 (yield 94%). ¹ H NMR (400 MHz, CD ₃ OD): δ8.00-7.70 (b, 4H, CH), 7.50-7.10 (b, 12H, CH), 4.20-3.90 (b, 12H, OCH ₃ ), 2.20- 2.00 (b, 4H, SiCH ₂ ), 1.50-1.00 (m, 32H, CH ₂ ), 0.90 (t, 3H, J = 6.8, CH ₃ ), 0.03 (t, 2H, J = 7.6, CH ₂ Si) , -0.29 (s, 3H, SiCH ₃ ) ppm.

Comparative Example 4 Synthesis of Catalyst with Non-Coordinating Anion CF ₃ CO ₂ ⁻

Silver trifluoroacetate (44.5 mg, 0.20 mmol) was used as a catalyst and a powder of yellow powder (107 mg) was obtained under the conditions and experimental methods of Comparative Example 1 (yield 93%). ¹ H NMR (400 MHz, CD ₃ OD): δ7.90-7.50 (b, 4H, CH), 7.40-7.00 (b, 12H, CH), 4.10-3.80 (b, 12H, OCH ₃ ), 2.10- 1.90 (b, 4H, SiCH ₂ ), 1.50-0.95 (m, 32H, CH ₂ ), 0.89 (t, 3H, J = 6.8, CH ₃ ), -0.02 (t, 2H, J = 6.8, CH ₂ Si ), -0.36 (s, 3H, SiCH ₃ ) ppm.

Comparative Example 5 Synthesis of Catalyst with Non-Coordinating Anion PF ₆ ⁻

Silver hexafluorophosphate (51.0 mg, 0.20 mmol) was used as a yellow powder catalyst (117 mg) under the conditions and experimental method of Comparative Example 1 (yield 96%). ¹ H NMR (400 MHz, CD ₃ OD): δ8.00-7.60 (b, 4H, CH), 7.40-7.20 (b, 12H, CH), 4.20-3.80 (b, 12H, OCH ₃ ), 2.30- 1.90 (b, 4H, SiCH ₂ ), 1.50-1.00 (m, 32H, CH ₂ ), 0.88 (t, 3H, J = 6.8, CH ₃ ), 0.02 (t, 2H, J = 7.2, CH ₂ Si) , -0.31 (s, 3H, SiCH ₃ ) ppm.

The catalysts of Comparative Examples 1-5 having different non-coordinating anions were synthesized and polymerized in the same manner as in Examples 4-6 (suspension stabilizer concentration was 0.14 wt% was used and the stirring speed was performed at 600 rpm). The results are shown in Table 6 below.

Comparative example	Negative ion	observe
One	ClO 4 -	No polymerization activity
2	CH 3 C 6 H 4 SO 3 -	No polymerization activity
3	CF 3 SO 3 -	No polymerization activity
4	CF 3 CO 2 -	No polymerization activity
5	PF 6 -	No polymerization activity

Through the above results, it can be confirmed that in order to achieve the object of the present invention, the anion of the palladium catalyst should be limited to RSO ₃ ⁻ having a high hydrophobic group.

Claims (15)

1. Compound represented by the following formula (1):
   [Formula 1]
   

   

   
   In Chemical Formula 1,
   R is (C6-C20) alkyl or (C6-C20) alkyl (C6-C20) aryl;
   n is an integer of 1 or 2;
   A is (C1-C20) alkyl or (C1-C20) acyl;
   Z is carbon or silicon;
   R ¹ and R ² are each independently (C ¹ -C 20) alkyl; (C1-C20) alkyl comprising at least one selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl comprising at least one selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl including one or more selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl comprising at least one selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkoxy; Or (C6-C30) aryloxy; R ¹ and R ² may be linked to each other to form a ring;
   Each R ³ is independently (C 1 -C 20) alkyl;
   R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently hydrogen; halogen; (C1-C20) alkyl; (C1-C20) alkyl comprising at least one selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl comprising at least one selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl including one or more selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl comprising at least one selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkoxy; (C6-C30) aryloxy; Formyl; (C1-C20) alkylcarbonyl; (C6-C20) arylcarbonyl; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl; Two or more of R ⁴ , R ⁵ , R ^6, and R ⁷ may be connected to each other to form a ring.
   
   
2. The method of claim 1,
   R is dodecylbenzene (C ₁₂ H ₂₅ C ₆ H _4- );
   n is 2;
   
   
3. The method of claim 1,
   R is dodecylbenzene (C ₁₂ H ₂₅ C ₆ H _4- );
   n is 2;
   Z is silicon;
   R ² and R ³ are methyl;
   R ⁴ to R ⁷ are hydrogen;
   R ¹ is —CH ₂ [CH ₂ ] _a CH ₃ , wherein a is an integer from 9 to 18.
   
   
4. Catalyst for carbon monoxide / olefin copolymerization represented by the formula (1):
   [Formula 1]
   

   

   
   In Chemical Formula 1,
   R is (C6-C20) alkyl or (C6-C20) alkyl (C6-C20) aryl;
   n is an integer of 1 or 2;
   A is (C1-C20) alkyl or (C1-C20) acyl;
   Z is carbon or silicon;
   R ¹ and R ² are each independently (C ¹ -C 20) alkyl; (C1-C20) alkyl comprising at least one selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl comprising at least one selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl including one or more selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl comprising at least one selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkoxy; Or (C6-C30) aryloxy; R ¹ and R ² may be linked to each other to form a ring;
   Each R ³ is independently (C 1 -C 20) alkyl;
   R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently hydrogen; halogen; (C1-C20) alkyl; (C1-C20) alkyl comprising at least one selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl comprising at least one selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl including one or more selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl comprising at least one selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkoxy; (C6-C30) aryloxy; Formyl; (C1-C20) alkylcarbonyl; (C6-C20) arylcarbonyl; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl; Two or more of R ⁴ , R ⁵ , R ^6, and R ⁷ may be connected to each other to form a ring.
   
   
5. The method of claim 4, wherein
   The copolymerization is carried out by a suspension polymerization method.
   
   
6. A method of preparing a polyketone by dissolving a compound represented by the following Chemical Formula 1 in an organic solvent and dispersing it in water to copolymerize carbon monoxide and an olefin having 2 to 20 carbon atoms:
   [Formula 1]
   

   

   
   
   
   In Chemical Formula 1,
   R is (C6-C20) alkyl or (C6-C20) alkyl (C6-C20) aryl;
   n is an integer of 1 or 2;
   A is (C1-C20) alkyl or (C1-C20) acyl;
   Z is carbon or silicon;
   R ¹ and R ² are each independently (C ¹ -C 20) alkyl; (C1-C20) alkyl comprising at least one selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl comprising at least one selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl including one or more selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl comprising at least one selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkoxy; Or (C6-C30) aryloxy; R ¹ and R ² may be linked to each other to form a ring;
   Each R ³ is independently (C 1 -C 20) alkyl;
   R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently hydrogen; halogen; (C1-C20) alkyl; (C1-C20) alkyl comprising at least one selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl comprising at least one selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl including one or more selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl comprising at least one selected from halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkoxy; (C6-C30) aryloxy; Formyl; (C1-C20) alkylcarbonyl; (C6-C20) arylcarbonyl; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl; Two or more of R ⁴ , R ⁵ , R ^6, and R ⁷ may be connected to each other to form a ring.
7. The method of claim 6,
   The organic solvent is an alcohol compound having 6 to 20 carbon atoms, a ketone compound having 6 to 20 carbon atoms, an ester compound having 6 to 20 carbon atoms, an ether compound having 5 to 20 carbon atoms, a haloalkene compound having 1 to 20 carbon atoms, and a 6 to 20 carbon atoms. 1 or 2 or more types selected from the group consisting of haloarene compounds.
   
   
8. The method of claim 6,
   Wherein said water comprises a suspension stabilizer.
   
   
9. The method of claim 8,
   The suspension stabilizer is one or two or more selected from the group consisting of polyvinylpyrrolidone (PVP), poly [(vinyl alcohol) -co- (vinylacetate)], natural gums, cellulose ethers and cellulose esters. How to.
   
   
10. The method of claim 6,
    The organic solvent is an alcohol compound having 6 to 20 carbon atoms;
    R is dodecylbenzene (C ₁₂ H ₂₅ C ₆ H _4- );
    n is two.
    
    
11. The method of claim 6,
    The organic solvent is an alcohol compound having 6 to 20 carbon atoms;
    R is dodecylbenzene (C ₁₂ H ₂₅ C ₆ H _4- );
    n is 2;
    Z is silicon;
    R ² and R ³ are methyl;
    R ⁴ to R ⁷ are hydrogen;
    R ¹ is —CH ₂ [CH ₂ ] _a CH ₃ , wherein a is an integer from 9 to 18.
    
    
12. The method of claim 8,
    The organic solvent is 1-octanol;
    The suspension stabilizer is poly [(vinyl alcohol) -co- (vinylacetate)];
    The olefin is ethylene, propylene or mixtures thereof;
    R is dodecylbenzene (C ₁₂ H ₂₅ C ₆ H _4- );
    n is 2;
    Z is silicon;
    R ² and R ³ are methyl;
    R ⁴ to R ⁷ are hydrogen;
    R ¹ is —CH ₂ [CH ₂ ] _a CH ₃ , wherein a is an integer from 9 to 18.
    
    
13. The method of claim 12,
    Wherein said poly [(vinyl alcohol) -co- (vinylacetate)] is prepared by partial hydrolysis of poly (vinylacetate) by 85 to 92%.
    
    
14. The method of claim 6,
    The polyketone is a spherical or granular polymer particles having a particle diameter of 0.02 ~ 2 mm, the bulk density is 0.20 g / mL ~ 0.30 g / mL production method characterized in that.
    
    
15. A polyketone having a bulk density of 0.20 to 0.30 g / mL, comprising spherical or granular polymer particles having a particle size of 0.02 to 2 mm, prepared by the method of any one of claims 6 to 14.
    
    

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