KR101074223B1 - Ethylene trimerization catalyst systems and method for preparing 1-hexene using the same - Google Patents

Abstract

A catalyst system comprising a PCCP framework ligand, a chromium-based metal compound, and an activator, wherein the catalyst system comprises (R ¹ ) (R ² ) P (R ⁵ ) CHCH (R ⁶ ) P (R ³ ) (R ⁴ ) The present invention relates to a method of producing 1-hexene with high activity and high selectivity while maintaining the reaction activity stably by trimerizing ethylene.

Hexene, ethylene, trimerization, catalysts, oligomers

Description

Ethylene trimerization catalyst systems and method for preparing 1-hexene using the same}

1 is a graph showing the change in catalyst activity over time in the ethylene trimerization reaction using the catalyst system according to the present invention.

Figure 2 is a graph showing the change in selectivity over time of the reaction in the ethylene trimerization reaction using the catalyst system according to the present invention.

The present invention relates to a catalyst system for use in the trimerization reaction of ethylene and to a process for producing 1-hexene by trimerizing ethylene using the catalyst system.

1-hexene is an important commercial raw material widely used in the polymerization process as a monomer or comonomer to make linear low density polyethylene as well as for use as a specific drug.

The preparation of the higher alphaolefins necessary for the production of linear low density polyethylene is obtained by oligomerization of ethylene. Ethylene oligomerization, however, has the inefficient aspect of producing a significant amount of butenes, other hexenes and hexenes isomers, certain higher oligomers and polyethylenes together.

Conventional oligomerization techniques of ethylene generally provide a variety of α-olefins depending on the Schulze-Flory or Poisson product distribution, so it was difficult to selectively produce only the desired product. In this regard, US Pat. No. 6,184,428 discloses a nickel catalyst comprising 2-diphenyl phosphino benzoic acid (DPPBA) as a chelating ligand, NiCl ₂ .6H ₂ O as a nickel precursor and sodium tetraphenylborate as a catalytic activator, In oligomerization of ethylene using this, the selectivity for linear C6 α-olefin was found to be about 33%.

In addition, German Patent No. 1,443,927 and US Patent No. 3,906,053 disclose Ziegler-type techniques based on trialkylaluminum catalysts, which have been shown to produce 14-25 mass% of 1-hexene for olefin mixtures. .

Recently, extensive research has been conducted on the production of 1-hexene by selective trimerization of ethylene through transition metal catalysis. Most known transition metal catalysts are chromium-based catalysts.

As the known chromium-based trimerization catalyst system, a catalyst system including a hetero atom ligand having a phosphorus and a nitrogen hetero atom or a hetero atom ligand having both a sulfur and a nitrogen hetero atom may be mentioned (WO 03/053891, WO 03 /). 053890). These ligands contain at least one carbon atom spacer between heteroatoms to form a substantial tridentate coordination with chromium, and chromium-based catalyst systems containing such ligands exhibit high selectivity for 1-hexene. Although it shows, there exists a problem that catalyst activity is not high.

On the other hand, WO 02/04119 discloses a chromium-based catalyst using a ligand of the general formula (R ¹ ) (R ² ) XYX (R ³ ) (R ⁴ ), wherein X is phosphorus, arsenic, or antimony , Y is a linking group such as -N (R ⁵ )-and at least one of R ¹ , R ² , R ³ and R ⁴ must have a polar or electron-donating substituent.

Another publication discloses (o-ethylphenyl) ₂ PN, a compound that does not have a polar substituent on at least one of R ¹ , R ² , R ³ and R ⁴ as a ligand that does not exhibit catalytic activity for 1-hexene under catalytic conditions. The use of (Me) P (o-ethylphenyl) ₂ is disclosed. (Antea Carter et al., Chem. Commun., 2002, p. 858-859).

In addition, according to Korean Patent Publication No. 10-2006-0002741, such as (o-ethylphenyl) ₂ PN (Me) P (o-ethylphenyl) ₂ The use of PNP ligands containing nonpolar substituents on the ortho position of the phenyl ring attached to phosphorus has shown that excellent ethylene trimerization activity and selectivity are indeed possible.

As such, the ligand of the chromium catalyst system for ethylene trimerization according to the prior art is limited to only PNP type hetero ligands of (R) _n PN (R ') P (R) _m , and selectivity and activity for 1-hexene All of these have technical limitations in that they do not present excellent catalyst systems. In addition, the ligand of the PNP-type backbone containing a hetero atom of the prior art has a problem that the reaction activity is not maintained consistently with the passage of the reaction time and the reaction rate is greatly reduced in the 1-hexene production reaction.

After repeated studies to solve the above problems of the prior art, the present inventors have studied the preparation of 1-hexene by ethylene trimerization through the action of a transition metal catalyst system using a PCCP skeletal structure ligand containing a phosphorus atom. In the heteroatom ligand, the structure between phosphorus and phosphorus atom was found to be an important factor in determining the selectivity and catalytic activity of 1-hexene. In addition, it was found that by using the P-C-C-P framework ligand according to the present invention, the activity of the catalyst is considerably stable to prevent a decrease in the reaction rate with the passage of the reaction time.

Accordingly, an object of the present invention is to stabilize the reaction activity by trimerizing ethylene using a transition metal or transition metal precursor, a cocatalyst, and a PCCP framework ligand represented by the following formula (1), and ethylene using the catalyst system. It is to provide a method for producing 1-hexene, which is highly active and highly selective.

Wherein R ¹ , R ² , R ³ and R ⁴ are independently hydrocarbyl, substituted hydrocarbyl, heterohydro carbyl, or substituted heterohydro carbyl, wherein R ¹ , R ² , R ³ and R ⁴ At least one of which has a substituent on at least one atom adjacent to the atom bonded to P,

R ⁵ and R ⁶ are selected from the group consisting of hydrocarbyl except substituted hydrogen, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydro carbyl.

Hereinafter, the present invention will be described in more detail.

The ethylene trimerization catalyst system according to the present invention comprises a transition metal or transition metal precursor, a P-C-C-P framework ligand and a promoter, and the P-C-C-P framework ligand is represented by the following formula (1).

[Formula 1]

Wherein R ¹ , R ² , R ³ and R ⁴ are independently hydrocarbyl, substituted hydrocarbyl or substituted heterohydro carbyl group, and these optional substituents are non-electron donors. These substituents may be nonpolar groups. Preferably, R ¹ , R ² , R ³ and R ⁴ may be substituted aromatic or substituted heteroaromatic groups which incorporate non-electron donors on atoms adjacent to atoms bonded to atom P. Suitable examples of R ¹ , R ² , R ³ and R ⁴ include methyl, ethyl, ethylenyl, propyl, propenyl, propynyl, butyl, cyclohexyl, 2-methylcyclohexyl, 2-ethylcyclohexyl, 2-iso Propylcyclohexyl, benzyl, phenyl, tolyl, xylyl, o-methylphenyl, o-ethylphenyl, o-isopropylphenyl, ot-butylphenyl, o-methoxyphenyl, o-isopropoxyphenyl, cumyl, mesityl , Biphenyl, naphthyl, anthracenyl, methoxy, ethoxy, phenoxy, tolyloxy, dimethylamino, thiomethyl, trimethylsilyl, dimethylhydrazyl, and the like. Preferably cyclohexyl, 2-methylcyclohexyl, 2-ethylcyclohexyl, 2-isopropylcyclohexyl, o-methylphenyl, o-ethylphenyl, o-isopropylphenyl, ot-butylphenyl, o-methoxyphenyl and o-isopropoxyphenyl may be independently selected.

R ¹ , R ² , R ³ and R ⁴ All may be aromatic or substituted aromatic groups, and R ¹ , R ² , R ³ and R ⁴ All may be substituted by non-electron donating groups on at least one atom adjacent to the atom bonded to each P atom, and R ¹ , R ² , R ³ and R ⁴ All may be substituted by nonpolar groups on at least one atom adjacent to the atom bonded to the P atom.

R ⁵ and R ⁶ are hydrocarbyl except substituted hydrogen, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydro carbyl groups. Specifically selected from the group consisting of aryl substituted by alkyl, aryloxy, halogen, nitro, alkoxycarbonyl, carbonyloxy, alkoxy, aminocarbonyl, carbonylamino, dialkylamino or derivatives thereof and optional substituents Can be.

PCCP framework ligands according to the invention may also be composed of multiple (R ¹ ) (R ² ) P (R ⁵ ) CHCH (R ⁶ ) P (R ³ ) (R ⁴ ) units. Examples of such multiple PCCP framework ligands include, but are not limited to, deaddrier ligands and ligands in which individual units are bound through one or more R groups, as typical examples of such ligands 1,2,4,5-tetra -(P (o-ethylphenyl) ₂ ) cyclohexane, 1,2,4,5-tetra- (P (o-ethylphenyl) ₂ ) benzene, 1,2,3,4-tetra- (P (o -Ethylphenyl) ₂ ) cyclopentane; and the like.

Examples of ligands according to the invention include (o-ethylphenyl) ₂ PCH (methyl) CH (methyl) P (o-ethylphenyl) ₂ , (o-isopropylphenyl) ₂ PCH (methyl) CH (methyl) P ( o-isopropylphenyl) ₂ , (o-methylphenyl) ₂ PCH (methyl) CH (methyl) P (o-methylphenyl) ₂ , (o-ethylphenyl) ₂ PCH (methyl) CH (methyl) P (phenyl) ₂ , (o-ethylphenyl) ₂ PCH (ethyl) CH (methyl) P (o-ethylphenyl) ₂ , (o-ethylphenyl) ₂ PCH (ethyl) CH (ethyl) P (o-ethylphenyl) ₂ , ( o-ethylphenyl) ₂ PCH (isopropyl) CH (methyl) P (o-ethylphenyl) ₂ , (o-ethylphenyl) ₂ PCH (n-propyl) CH (methyl) P (o-ethylphenyl) ₂ , (o-ethylphenyl) ₂ PCH (isopropyl) CH (ethyl) P (o-ethylphenyl) ₂ , 1,2-di- (P (o-ethylphenyl) ₂ ) cyclohexane, 1,2-di- (P (o-ethylphenyl) ₂ ) cyclopentane, 3,4-di- (P (o-ethylphenyl) ₂ ) pyrrole, 4,5-di- (P (o-ethylphenyl) ₂ ) imidazole, (o-ethylphenyl) ₂ PCH (dimethylamine) CH (dimethylamine) P (o-ethylphenyl) ₂ , (o-methoxyphenyl) ₂ PCH (methyl) CH (methyl) P (o-methoxyphenyl) ₂ , (o-ethoxyphenyl) ₂ PCH (methyl) CH (Methyl) P (o-ethoxyphenyl) ₂ , (o-dimethylaminephenyl) ₂ PCH (methyl) CH (methyl) P (o-dimethylaminephenyl) ₂ , (o-ethylcyclohexyl) ₂ PCH (methyl ) CH (methyl) P (o-ethylcyclohexyl) ₂ , but is not limited thereto, and the ligands according to the present invention may be prepared using various methods known to those skilled in the art.

The PCCP-type framework of the ligand according to the present invention has a structure independent of the known conventional (R) _n PN (R ') P (R) _m heteroligand, and is heterologous within the framework of the ligand. The only atom is the phosphorus (P) atom. That is, the ligand used in the catalyst system according to the present invention is composed of two carbon-carbon skeleton structures without nitrogen atoms between two phosphorus atoms, and exhibits excellent catalytic activity by appropriately adjusting the spatial structure with substituents around carbon. As well as high 1-hexene selectivity above 85 wt%.

The catalyst system comprising the ligand according to the present invention for the production of high selectivity 1-hexene can be prepared by combining the transition metal compound and the promoter in any order. The catalyst system according to the present invention can be prepared through the step of generating in situ ligand coordination complex from the transition metal compound and the ligand of the PCCP skeleton structure, the preformed configuration prepared using the ligand and transition metal compound of the PCCP skeleton structure The complex may be added to the reaction mixture, or the ligand and transition metal compound of the PCCP skeletal structure may be separately added to the reactor to generate a ligand coordination complex of the PCCP skeletal structure in situ. Generating ligand coordination complexes of PCCP framework structures in situ means that the complexes are produced in the medium in which the catalysis takes place. In order for coordination complexes to be formed in situ, the ratio of metal to ligand is typically about 0.01: 1 to The ligand of the transition metal compound and the PCCP skeletal structure is combined to be 100: 1, preferably about 0.1: 1 to 10: 1, more preferably 0.5: 1 to 2: 1.

The transition metal used in the catalyst system according to the invention may be selected from chromium, molybdenum, tungsten, titanium, tantalum, vanadium and zirconium, preferably chromium. The transition metal compound catalyzing the ethylene trimerization according to the present invention may be a simple inorganic or organic salt, coordination or organometallic complex, preferably the compound is chromium or chromium precursor, and the chromium or chromium precursor is chromium ( III) acetylacetonoate, chromium trichloride tristetrahytrofuran and chromium (III) 2-ethylhexanoate are preferred.

In addition, the P-C-C-P skeletal structure ligand coordination complex of the transition metal is dissolved at room temperature or higher, but may be modified into a form attached to the polymer chain to be insoluble. In addition, a ligand or a transition metal compound having a P-C-C-P skeleton structure may be immobilized by binding to a backbone such as silica, silica gel, polysiloxane, or alumina.

The promoter for use in the method of the present invention may be any compound which produces an active catalyst upon mixing with a ligand of the P-C-C-P backbone structure and a transition metal compound. The active agent may be not only a single compound but also a mixture thereof, and preferred examples thereof include organoaluminum compounds, organoboron compounds, and organic salts.

The organoaluminum compounds include compounds of the formula AlR ₃ (R each independently is C ₁ to C ₁₂ alkyl, oxygen containing alkyl or halide), compounds such as LiAlH _4, and the like. Examples include trimethylaluminum (TMA), triethylaluminum (TEA), triisobutylaluminum (TIBA), tri-n-octylaluminum, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum chloride, diethylaluminum chloride, Aluminum isopropoxide, ethylaluminum sesquichloride, methylaluminum sesquichloride and aluminoxanes. Aluminoxanes are well known in the art as oligomeric compounds that can be prepared by mixing water with alkylaluminum compounds such as trimethylaluminum. The aluminoxane oligomeric compounds may be in linear, cyclic, cage form, or mixtures thereof, and may be in the form of a mixture of two or more different aluminoxanes.

Examples of the organoboron compound include boroxine, NaBH ₄ , triethyl borane, triphenylborane, triphenylborane ammonia complex, tributylborate, triisopropylborate, tris (pentafluorophenyl) borane, and trityl (tetrapenta). Florophenyl) borate, dimethylphenylammonium (tetrapentafluorophenyl) borate, diethylphenylammonium (tetrapentafluorophenyl) borate, methyldiphenylammonium (tetrapentafluorophenyl) borate, ethyldiphenylammonium (tetra Pentafluorophenyl) borate, and the like, and these organoboron compounds may be used in a mixed form with the organoaluminum compounds.

Also among the cocatalyst components usable in the catalyst system according to the invention are aluminoxanes modified alkyl aluminoxanes such as methyl aluminoxane (MAO) and ethyl aluminoxane (EAO) as well as modified alkyl aluminoxanes (MMAO). It may be selected from noric acid. Modified methyl aluminoxane (from Akzo Nobel) contains a mixed alkyl group such as isobutyl or n-octyl group in addition to the methyl group.

The aluminoxane may be formulated in a ratio of about 1: 1 to 10,000: 1, preferably about 1: 1 to 1,000: 1, of aluminum: metal when combined with transition metal compounds, particularly chromium compounds.

The individual components of the catalyst system according to the invention can be combined in the presence or absence of a solvent, simultaneously or sequentially in any order. Mixing of each catalyst component can be carried out at a temperature of -20 to 250 ° C., and the presence of olefins during the mixing of the catalyst components can provide a protective effect to provide improved catalyst performance. Preferable temperature range is 20-100 degreeC.

The reaction product according to the invention, i.e. 1-hexane, is a homogeneous liquid phase reaction in the presence or absence of an inert solvent, or a slurry reaction in which the catalyst system is partially or completely insoluble using conventional catalysts and contacting techniques with the disclosed catalyst system. Alternatively, the biphasic liquid / liquid reaction or product olefins can be prepared by bulk or gas phase reactions serving as the main medium.

If the process for producing 1-hexene using the catalyst system according to the invention is also carried out in an inert solvent, any inert solvent which does not react with each catalyst compound and promoter can be used. These inert solvents may include any saturated aliphatic and unsaturated aliphatic and aromatic hydrocarbons and halogenated hydrocarbons, preferably benzene, toluene, xylene, cumene, heptane, cyclohexane, methylcyclohexane, methylcyclopentane, n-hexane , 1-hexene, 1-hexene, and the like, but are not limited thereto.

The method for preparing 1-hexene using the catalyst system according to the present invention may be carried out at a temperature range of -20 to 250 ° C, preferably 15 to 130 ° C, more preferably 30 to 70 ° C. The reaction pressure can be carried out at atmospheric pressure to a pressure of 500 bar, preferably at an ethylene pressure of 10 to 70 bar, more preferably at a pressure of 30 to 50 bar.

In a preferred embodiment of the invention the ligand coordination complex of the P-C-C-P framework structure and the reaction conditions are selected such that the 1-hexene yield from ethylene is at least 30 mass%, preferably at least 50 mass%. Yield in this case means mass fraction of 1-hexene relative to the total mass of the reaction product formed. The process according to the invention also depends on the ligand of the PCCP backbone structure and the reaction conditions, in addition to 1-hexene which is a trimer of ethylene, some 1-butene, 1-octene, methylcyclopentane, methylenecyclopentane, propylcyclopentane and many higher Oligomers and polyethylenes can be provided.

The process according to the method can be carried out in a plant comprising any type of reactor, examples of which include, but are not limited to, batch reactors, semi-batch reactors and continuous reactors. The plant may comprise a reactor, an inlet of an olefin reactor and a catalyst system therein, a combination of the oligomerization reaction product from this reactor and a line for effluent and at least one separator for separating the oligomerization reaction product.

By trimerizing ethylene using the ethylene trimerization catalyst system according to the invention, it is possible to produce 1-hexene with high activity and high selectivity while maintaining stable reaction activity.

Hereinafter, the present invention will be described in more detail with reference to Preparation Examples and Examples, but the scope of the present invention is not limited thereto.

Example

catalyst Manufacturing example  One: R, R -( 2 - Methoxyphenyl ) ₂ PCH ( methyl ) CH ( methyl ) P ( 2 - Methoxyphenyl ) ₂ Ligand  Produce

In B. Bosnich et al, J. Am. Chem. Prepared as disclosed in Soc 99 (19) (1977) 6262.

(2R, 3R) -butanediol di-p-toluenesolfonate was prepared from (2R, 3R) -butanediol. This method of preparation is described in RB Mitra et al, J. Am . Chem . Soc . 84 (1962). 100 ml (1.24 mol) of dried pyridine was added to a 1 L flask cooled in an ice water bath, mixed with 100 g (0.525 mol) of p -toluene sulphonyl chloride, and then slowly added dropwise to 22 ml (0.245 mol) of (2R, 3R) -butanediol. It was. After raising the temperature to room temperature for 20 minutes, the mixture of the semi-solid phase was kept at room temperature overnight. Excess ice cubes were added and shaken vigorously to prevent lumps from forming. After confirming that the powder crystals were slowly separated, the mixture was stirred for 2 hours with ice cubes, and 70 ml of broken ice cubes and concentrated hydrochloric acid solution were poured into the mixture with vigorous stirring. The extracted slurry was filtered, washed thoroughly with water and dried to give 85 g (86.3%) of (2R, 3R) -butanediol di-p -toluenesolfonate (melting point 62-64 ° C.).

The preparation of tri ( 2 -methoxyphenyl) yne was carried out as follows. A piece of magnesium (91.1 g, 3.75 mol) was added dropwise to 95 ml (0.75 mol) of 2- bromo-anisol in 2 L of THF. After vigorous reaction, the reaction mixture was heated at reflux for 2 hours to obtain Grignard reagent. This Grignard reagent was added dropwise over 2 hours with stirring to 17.5 ml (0.2 mol) of a PCl ₃ solution in 2 L of THF at -78 ° C. After completion of the dropwise addition, the dry ice / acetone bath was removed and the reaction raised to room temperature. The reaction was stirred overnight and the solvent was removed in vacuo. All were used in the next step without this phosphine product removal.

In a 3-necked 1 L round flask equipped with 250 ml drop-in fornell, reflux condenser and nitrogen injector, 70 g of recrystallized tri (2-methoxyphenol) and 300 ml of dried tetrahydrofuran (THF) Injected. 2.8 g of thin lithium flakes were added to this solution in a nitrogen atmosphere with stirring at 25 ° C. As soon as LiP (2-OMe-Ph) ₂ was formed in the solution, a lot of heat was generated and the solution turned dark red yellow. The temperature was slowly raised to 55 ° C. for 1 hour and stirred while cooling to 25 ° C. for 2 hours. The 2-methoxyphenyllithium formed was decomposed by dropwise addition of 18.5 g of distilled and purified t-butylchloride for 45 minutes. The clear red yellow solution was boiled for 5 minutes and then cooled to -4 ° C.

To this was added 19.6 g of (2R, 3R) -butanediol di-p-toluenesolfonate prepared above in 100 ml of dried THF, under cooling and stirring, for 1 hour. After slowly raising to room temperature, the mixture was stirred for 30 minutes. After adding 300 ml of nitrogen-dried water, THF was distilled off under reduced pressure, and the product of colorless oil was extracted. The product was extracted twice with 150 mL ether and dried by Na ₂ SO ₄ . The ether extract was filtered under a nitrogen into a solution of 8.4 g of nickel perchlorate hexahydrate in 50 ml of ethanol. Na ₂ SO ₄ remaining in the filter was thoroughly washed with ether, and the ether solution was added to the nickel solution. The product in reddish brown oil form, sometimes showing yellow crystals, is [Ni ((2S, 3S) -bis (di-p-methoxyphenyl) phosphorousbutane) ₂ ] (ClO ₄ ) ₂ . This oil crystal mixture was added to 8.4 g of sodium oxycyanite (NaNCS) dissolved in hot ethanol (50 mL) and the solution was added to a uniform tan solid [Ni ((2S, 3S) -bis (di- o -meth). Oxyphenyl) phosphorusbutane) ₂ Stirred vigorously for several hours until NCS] NCS was formed. This solid product was washed thoroughly with ethanol and finally with ether.

17 g of this nickel complex was suspended in nitrogen with 150 ml of ethanol and heated with stirring. 4 g of sodium cyanide (NaCN) were quickly added to 20 g of water. The nickel complex was slowly dissolved to form a clear red solution [Ni ((2S, 3S) -bis ( di - o- methoxyphenyl) phosphorousbutane) ₂ CN ₃ ] ^- , which was then converted to a beige turbid solution. The hot solution was stirred until a yellow slurry. The slurry solution was cooled and the solid washed 25 ml twice successively with water and then quickly cooled with ice-cooled ethanol. The beige solid containing impurities was dried at 25 ° C., added with 125 mL of anhydrous ethanol, and filtered through frittes. The fritted filtration was maintained at room temperature for 12 hours, and the filtrate was lost and only a colorless, glossy solid remained. Pure S, S of completely colorless again crystallized in absolute ethanol 60 ㎖ - (2 - methoxyphenyl) ₂ PCH (methyl) CH (methyl) P (2 - methoxyphenyl) ₂ was obtained for the 6.8 g.

Example  One: Cr ( III ) ( Acetylacetonoate ) ₃ , (2- Methoxyphenyl ) ₂ P-CH ( methyl ) CH ( methyl ) -P (2- Methoxyphenyl ) ₂   And MAO Ethylene Using Trimerization  reaction

The 300 ml stainless steel reactor was washed with nitrogen and vacuum, and then 100 ml of cyclohexane was added, 4.0 mmol-Al of MAO was added, and the temperature was raised to 45 ° C. In a glove box, 3.5 mg (0.010 mmol) of Cr (III) (acetylacetonoate) _{3 in} 10 ml of toluene were taken in a 50 ml Schlenk container, and (2-methoxyphenyl) ₂ P-CH ( Methyl) CH (methyl) -P (2-methoxyphenyl) ₂ 5.5 mg (0.010 mmol) was mixed and stirred at room temperature for 5 minutes and then added to the reactor. The pressure reactor was filled with ethylene at 30 bar and stirred at a stirring speed of 600 rpm. After 30 minutes the ethylene feed to the reactor was stopped, stirring was stopped to stop the reaction and the reactor was cooled down below 10 ° C.

After releasing excess ethylene in the reactor, ethanol mixed with 10 vol% hydrochloric acid was injected into the liquid contained in the reactor. Nonan was added as an internal standard to analyze the liquid phase by GC-FID. A small amount of organic layer sample was dried over anhydrous magnesium sulfate and analyzed by GC-FID. The remaining organic layer was filtered to separate the solid wax / polymer product. These solid products were dried overnight in an oven at 100 ° C. and weighed to give 0.63 g of polyethylene. GC analysis confirmed that the total mass of the reaction mixture was 56.2 g. The product distribution of this example is summarized in Table 1.

Example  2: Cr ( III ) ( Acetylacetonoate ) ₃ , (2- Methoxyphenyl ) ₂ P-CH ( methyl ) CH ( methyl ) -P (2- Methoxyphenyl ) ₂  And MAO Ethylene Using Trimerization  reaction

The 300 ml stainless steel reactor of Example 1 was washed with nitrogen and vacuum, and then 100 ml of cyclohexane was added, followed by addition of MAO 2.0 mmol-Al, and the temperature was raised to 45 ° C. In a glove box, 1.7 mg (0.005 mmol) of Cr (III) (acetylacetonoate) _{3 in} 10 ml of toluene were taken in a 50 ml Schlenk container, and (2-methoxyphenyl) ₂ P-CH ( 2.73 mg (0.005 mmol) of methyl) CH (methyl) -P (2-methoxyphenyl) ₂ was mixed and stirred at room temperature for 5 minutes and then added to the reactor. The pressure reactor was filled with ethylene at 30 bar and stirred at a stirring speed of 600 rpm. After 30 minutes the ethylene feed to the reactor was stopped, stirring was stopped to stop the reaction and the reactor was cooled down below 10 ° C.

After releasing excess ethylene in the reactor, ethanol mixed with 10 vol% hydrochloric acid was injected into the liquid contained in the reactor. Nonan was added as an internal standard to analyze the liquid phase by GC-FID. A small amount of organic layer sample was dried over anhydrous magnesium sulfate and analyzed by GC-FID. The remaining organic layer was filtered to separate the solid wax / polymer product. After drying these solid products overnight in a 100 ° C. oven, the mass of the product identified by GC analysis was 73.5 g and the product distribution of this example is summarized in Table 1.

Example  3: Cr ( III ) ( Acetylacetonoate ) ₃ , (2- Methoxyphenyl ) ₂ P-CH ( methyl ) CH ( methyl ) -P (2- Methoxyphenyl ) ₂  And MAO Ethylene Using Trimerization  reaction

The 300 ml stainless steel reactor of Example 1 was washed with nitrogen and vacuum, and then 100 ml of cyclohexane was added, followed by addition of MAO 2.0 mmol-Al, and the temperature was raised to 45 ° C. In a glove box, 1.7 mg (0.005 mmol) of Cr (III) (acetylacetonoate) ₃ in 10 ml of toluene were taken in a 50 ml Schlenk container, and (methoxyphenyl) ₂ PCH (methyl) CH ( 2.73 mg (0.005 mmol) of methyl) P (methoxyphenyl) ₂ was mixed and stirred at room temperature for 5 minutes and then added to the reactor. The temperature of the reactor was raised to 70 ° C. and maintained, and the pressure reactor was filled with ethylene at 30 bar and stirred at a stirring speed of 600 rpm. After 30 minutes the ethylene feed to the reactor was stopped, stirring was stopped to stop the reaction and the reactor was cooled down below 10 ° C.

After releasing excess ethylene in the reactor, ethanol mixed with 10 vol% hydrochloric acid was injected into the liquid contained in the reactor. Nonan was added as an internal standard to analyze the liquid phase by GC-FID. A small amount of organic layer sample was dried over anhydrous magnesium sulfate and analyzed by GC-FID. The remaining organic layer was filtered to separate the solid wax / polymer product. After drying these solid products in an oven at 100 ° C. overnight, the mass of the product identified by GC analysis was 48.6 g and the product distribution of this example is summarized in Table 1.

Example  4: CrCl ₃ ( Tetrahydrofuran ) ₃ , (2- Methoxyphenyl ) ₂ P- CH ( methyl ) CH (Methyl) -P (2-meth Toxi Phenyl) ₂ And MAO Ethylene Using Trimerization  reaction

The 300 ml stainless steel reactor of Example 1 was washed with nitrogen and vacuum, and then 100 ml of cyclohexane was added, 4.0 mmol-Al of MAO was added, and the temperature was raised to 45 ° C. In a glove box, 3.75 mg (0.01 mmol) of CrCl ₃ (tetrahydrofuran) _{3 in} 10 ml of toluene was taken in a 50 ml Schlenk container, and (2-methoxyphenyl) ₂ P-CH (methyl) CH of the catalyst preparation example 1 was prepared. 5.5 mg (0.01 mmol) of (methyl) -P (2-methoxyphenyl) ₂ was mixed and stirred at room temperature for 5 minutes and then added to the reactor. The pressure reactor was filled with ethylene at 30 bar and stirred at a stirring speed of 600 rpm. After 30 minutes the ethylene feed to the reactor was stopped, stirring was stopped to stop the reaction and the reactor was cooled down below 10 ° C.

After releasing excess ethylene in the reactor, ethanol mixed with 10 vol% hydrochloric acid was injected into the liquid contained in the reactor. Nonan was added as an internal standard to analyze the liquid phase by GC-FID. A small amount of organic layer sample was dried over anhydrous magnesium sulfate and analyzed by GC-FID. The remaining organic layer was filtered to separate the solid wax / polymer product. After drying these solid products overnight in a 100 ° C. oven, the mass of the product identified by GC analysis was 38.2 g and the product distribution of this example is summarized in Table 1.

Example  5: Cr (2- Ethylhexanoate ) _3,   (2- Methoxyphenyl ) ₂ P- CH ( methyl ) CH (Methyl) -P (2-meth Toxi Phenyl) ₂   And MAO Ethylene Using Trimerization  reaction

The 300 ml stainless steel reactor of Example 1 was washed with nitrogen and vacuum, and then 100 ml of cyclohexane was added, 4.0 mmol-Al of MAO was added, and the temperature was raised to 45 ° C. In a glove box, a Schlenk vessel in 50㎖ toluene 10㎖ Cr (2-ethylhexanoate) takes a ₃ 4.0 mg (0.01 m㏖), prepared in Catalyst Preparation Example 1 (2-methoxyphenyl) ₂ P-CH (methyl ) 5.5 mg (0.01 mmol) of CH (methyl) -P (2-methoxyphenyl) ₂ was mixed and stirred at room temperature for 5 minutes and then added to the reactor. The pressure reactor was filled with ethylene at 30 bar and stirred at a stirring speed of 600 rpm. After 30 minutes the ethylene feed to the reactor was stopped, stirring was stopped to stop the reaction and the reactor was cooled down below 10 ° C.

After releasing excess ethylene in the reactor, ethanol mixed with 10 vol% hydrochloric acid was injected into the liquid contained in the reactor. Nonan was added as an internal standard to analyze the liquid phase by GC-FID. A small amount of organic layer sample was dried over anhydrous magnesium sulfate and analyzed by GC-FID. The remaining organic layer was filtered to separate the solid wax / polymer product. After drying these solid products in an oven at 100 ° C. overnight, the mass of the product identified by GC analysis was 65.7 g and the product distribution of this example is summarized in Table 1.

catalyst Manufacturing example  2: R, R- (2- Ethylphenyl ) ₂ P- CH ( methyl ) CH (Methyl) -P (2- Ethylphenyl ) ₂ Ligand  Produce

A ligand was prepared in the same manner as in Preparation Example 1, except that 2-bromo ethylbenzene was used instead of 2-bromo-anisole to prepare tri (2-ethylphenyl) in.

Example  6: Cr ( III ) ( Acetylacetonoate ) ₃ , R, R- (2- Ethylphenyl ) ₂ P-CH ( methyl ) CH ( methyl ) -P (2- Ethylphenyl ) ₂  And MAO Ethylene Using Trimerization  reaction

The 300 ml stainless steel reactor of Example 1 was washed with nitrogen and vacuum, and then 100 ml of cyclohexane was added, 4.0 mmol-Al of MAO was added, and the temperature was raised to 45 ° C. In a glove box, 3.5 mg (0.010 mmol) of Cr (III) (acetylacetonoate) _{3 in} 10 ml of toluene were taken in a 50 ml Schlenk container, and R, R- (2-ethylphenyl) ₂ P of Catalyst Preparation Example 2 was obtained. 5.4 mg (0.010 mmol) of -CH (methyl) CH (methyl) -P (2-ethylphenyl) ₂ was mixed and stirred at room temperature for 5 minutes and then added to the reactor. The pressure reactor was filled with ethylene at 30 bar and stirred at a stirring speed of 600 rpm. After 30 minutes the ethylene feed to the reactor was stopped, stirring was stopped to stop the reaction and the reactor was cooled down below 10 ° C.

After releasing excess ethylene in the reactor, ethanol mixed with 10 vol% hydrochloric acid was injected into the liquid contained in the reactor. Nonan was added as an internal standard to analyze the liquid phase by GC-FID. A small amount of organic layer sample was dried over anhydrous magnesium sulfate and analyzed by GC-FID. The remaining organic layer was filtered to separate the solid wax / polymer product. These solid products were dried in an oven at 100 ° C. overnight and then weighed to yield 1.5 g of polyethylene. GC analysis confirmed that the total mass of the reaction mixture was 86.3 g. The product distribution of this example is summarized in Table 1.

Example  7: CrCl ₃ ( Tetrahydrofuran ) ₃ , R, R- (2- Ethylphenyl ) ₂ P- CH ( methyl ) CH (Methyl) -P (2- Ethylphenyl ) ₂ And MAO Ethylene Using Trimerization  reaction

The 300 ml stainless steel reactor of Example 1 was washed with nitrogen and vacuum, and then 100 ml of cyclohexane was added, 4.0 mmol-Al of MAO was added, and the temperature was raised to 45 ° C. In a glove box, 3.75 mg (0.01 mmol) of CrCl ₃ (tetrahydrofuran) _{3 in} 10 ml of toluene was taken in a 50 ml Schlenk container, and R, R- (2-ethylphenyl) ₂ P-CH ( Methyl) CH (methyl) -P (2-ethylphenyl) ₂ 5.4 mg (0.01 mmol) was mixed and stirred at room temperature for 5 minutes and then added to the reactor. The pressure reactor was filled with ethylene at 30 bar and stirred at a stirring speed of 600 rpm. After 30 minutes the ethylene feed to the reactor was stopped, stirring was stopped to stop the reaction and the reactor was cooled down below 10 ° C.

After releasing excess ethylene in the reactor, ethanol mixed with 10 vol% hydrochloric acid was injected into the liquid contained in the reactor. Nonan was added as an internal standard to analyze the liquid phase by GC-FID. A small amount of organic layer sample was dried over anhydrous magnesium sulfate and analyzed by GC-FID. The remaining organic layer was filtered to separate the solid wax / polymer product. After drying these solid products overnight in a 100 ° C. oven, the mass of the product identified by GC analysis was 50.8 g and the product distribution of this example is summarized in Table 1.

Example  8: Cr (2- Ethylhexanoate ) _3,  R, R- (2- Ethylphenyl ) ₂ P- CH ( methyl ) CH (Methyl) -P (2-on Teal Phenyl) ₂ And MAO Ethylene Using Trimerization  reaction

The 300 ml stainless steel reactor of Example 1 was washed with nitrogen and vacuum, and then 100 ml of cyclohexane was added, 4.0 mmol-Al of MAO was added, and the temperature was raised to 45 ° C. In a glove box, a Schlenk vessel in 50㎖ toluene 10㎖ Cr (2-ethylhexanoate) takes a _{3 4.0 mg (0.01 m㏖),} R, R- , prepared in Catalyst Preparation Example 2 (2-ethylphenyl) ₂ P- 5.4 mg (0.01 mmol) of CH (methyl) CH (methyl) -P (2-ethylphenyl) ₂ was mixed and stirred at room temperature for 5 minutes and then added to the reactor. The pressure reactor was filled with ethylene at 30 bar and stirred at a stirring speed of 600 rpm. After 30 minutes the ethylene feed to the reactor was stopped, stirring was stopped to stop the reaction and the reactor was cooled down below 10 ° C.

After releasing excess ethylene in the reactor, ethanol mixed with 10 vol% hydrochloric acid was injected into the liquid contained in the reactor. Nonan was added as an internal standard to analyze the liquid phase by GC-FID. A small amount of organic layer sample was dried over anhydrous magnesium sulfate and analyzed by GC-FID. The remaining organic layer was filtered to separate the solid wax / polymer product. After drying these solid products overnight in a 100 ° C. oven, the mass of the product identified by GC analysis was 75.7 g and the product distribution of this example is summarized in Table 1.

Ethylene trimerization reaction DML implementation result Total output
(g) Activity
(Kg / g-Cr) 1-hexene
(%) 1-octene
(%) 1-decene
(%) Etc
(%) polymer
(%) Example 1 56.2 108.1 91.1 3.4 2.5 1.9 1.1 Example 2 73.5 282.7 93.6 2.7 1.5 1.3 0.9 Example 3 48.6 187.0 73.1 2.1 10.3 9.3 5.2 Example 4 38.2 73.5 88.6 2.6 5.2 2.2 1.4 Example 5 65.7 126.3 90.6 2.5 4.5 1.4 1.5 Example 6 86.3 166.0 87.5 3.6 5.7 1.5 1.7 Example 7 50.8 97.7 89.5 3.1 5.1 1.7 1.0 Example 8 75.7 145.6 90.3 2.3 3.2 3.5 0.7

Examples 9-12 Cr (III) (acetylacetonoate) ₃ , (2-methoxyphenyl) ₂ P-CH (methyl) CH (methyl) -P (2-methoxyphenyl) ₂ and MMAO-12 Changes in Reaction Activity and Selectivity with Reaction Time of Ethylene Trimerization Using

The reaction temperature was maintained at 45 ° C., the ethylene pressure was maintained at 30 bar, 1.75 mg (0.005 mmol) of Cr (III) (acetylacetonoate) ₃ , (2-methoxyphenyl) ₂ P-CH of catalyst preparation example 1 2.73 mg (0.005 mmol) of (methyl) CH (methyl) -P (2-methoxyphenyl) ₂ and 3.0 mmol of MMAO-12 from Akzo-Nobel were used for a reaction time of 30 minutes according to each example (Example 9), 1 hour (Example 10), 2 hours (Example 11) and 4 hours (Example 12) were carried out with different reactions. Other reaction and product processing proceeded in the same manner as in Example 1.

The reactant production results are shown in Table 2 below, and the changes in activity and selectivity over time are shown in FIGS. 1 and 2.

Comparative Example  1 to 4: Cr ( III ) ( Acetylacetonoate ) ₃ , (2- Methoxyphenyl ) ₂ PN (Isopropyl) P (2- Methoxyphenyl ) ₂   And MMAO - 12  Used ethylene Trimerization  Changes in reaction activity and selectivity with reaction time of reaction

(2-methoxyphenyl) ₂ P-CH (methyl) CH (methyl) -P (2-methoxyphenyl) ₂ instead of (2-methoxyphenyl) ₂ PN (isopropyl) P (2-methoxyphenyl) ₂ The procedure was carried out in the same manner as in Examples 9 to 12, except that 2.68 mg (0.005 mmol) was used.

The reactant production results are shown in Table 2 below, and the changes in activity and selectivity over time are shown in FIGS. 1 and 2.

Results of the comparison of the reaction time of ethylene trimerization reaction Reaction time
(hr) Total output
(g) 1-hexene
(%) 1-octene
(%) 1-decene
(%) polymer Example 9 0.5 71.2 92.2 3.3 2.3 1.3 Example 10 One 104.5 91.3 3.2 4.5 0.8 Example 11 2 172.3 90.5 2.4 3.6 2.0 Example 12 4 248.6 89.2 2.6 5.2 1.8 Comparative Example 1 0.5 76.3 93.2 3.6 2.9 1.5 Comparative Example 2 One 89.5 92.3 3.4 3.4 0.7 Comparative Example 3 2 100.6 91.6 3.4 3.3 2.5 Comparative Example 4 4 120.3 89.5 3.6 4.0 3.4

Examples 9 to 12 and Comparative Examples 1 to 4 compare the performance of the 1-hexene preparation reaction according to the reaction time in the ligand of the PCCP skeleton structure of the present invention and the PNP ligand of the prior art hetero atom structure. It is for.

Figure 1 shows the change in catalyst activity over time of the reaction of the ethylene trimerization reaction, in the case of using the catalyst system of the ligand of the PCCP structure according to the present invention was able to obtain a consistently increased yield over time, When the PNP ligand catalyst system according to the technique is used, the yield initially increases, but it can be seen that the yield decreases as the reaction proceeds. That is, it can be seen that the P-C-C-P ligand catalyst system according to the present invention has an effect of stably maintaining catalytic activity as compared to the PNP ligand catalyst system according to the prior art.

Figure 2 is a graph showing the change in selectivity over the reaction time of the ethylene trimerization reaction, the selectivity in the case of using the ligand catalyst system of the PCCP structure according to the present invention and the PNP ligand catalyst system according to the prior art There was no significant difference.

That is, in the ethylene trimerization reaction, it can be seen that the PCCP ligand catalyst system according to the present invention can maintain the reaction activity more stably than the conventional catalyst system, while having the same high activity and selectivity as the conventional PNP ligand catalyst system. .

In the case of trimerization of ethylene using a chromium-based catalyst system containing a PCCP framework ligand according to the present invention, it has excellent catalytic activity and high selectivity for 1-hexene, thereby making it possible to prepare high purity 1-hexene. In addition, since the catalytic activity is stably maintained, there is an excellent effect of preventing a decrease in the reaction rate with the passage of the reaction time.

Claims (10)

Ethylene trimerization catalyst system comprising a transition metal or transition metal precursor, a promoter and a P-C-C-P framework ligand represented by the following formula (1). [Formula 1]

The PCCP framework ligand is (o-ethylphenyl) ₂ PCH (methyl) CH (methyl) P (o-ethylphenyl) ₂ , (o-isopropylphenyl) ₂ PCH (methyl) CH (methyl) P (o- Isopropylphenyl) ₂ , (o-methylphenyl) ₂ PCH (methyl) CH (methyl) P (o-methylphenyl) ₂ , (o-ethylphenyl) ₂ PCH (methyl) CH (methyl) P (phenyl) ₂ , ( o-ethylphenyl) ₂ PCH (ethyl) CH (methyl) P (o-ethylphenyl) ₂ , (o-ethylphenyl) ₂ PCH (ethyl) CH (ethyl) P (o-ethylphenyl) ₂ , (o- Ethylphenyl) ₂ PCH (isopropyl) CH (methyl) P (o-ethylphenyl) ₂ , (o-ethylphenyl) ₂ PCH (n-propyl) CH (methyl) P (o-ethylphenyl) ₂ , (o -Ethylphenyl) ₂ PCH (isopropyl) CH (ethyl) P (o-ethylphenyl) ₂ , 1,2-di- (P (o-ethylphenyl) ₂ ) cyclohexane, 1,2-di- (P (o-ethylphenyl) ₂ ) cyclopentane, 3,4-di- (P (o-ethylphenyl) ₂ ) pyrrole, 4,5-di- (P (o-ethylphenyl) ₂ ) imidazole, (o -Ethylphenyl) ₂ PCH (dimethylamine) CH (dimethylamine) P (o-ethylphenyl) ₂ , (o-methoxyphenyl) ₂ PCH (methyl) CH (methyl) P (o-methoxyphenyl) ₂ , (in o- methoxyphenyl) ₂ PCH (methyl) CH (methoxy ) P (o- methoxyphenyl) _2, (o- dimethylamine phenyl) ₂ PCH (methyl) CH (methyl) P (o- dimethylamine phenyl) _2, and (o- ethyl-cyclohexyl) ₂ PCH (methyl) CH (methyl) P (o-ethylcyclohexyl) ₂ is selected from the group consisting of. delete delete delete delete delete The ethylene trimerization catalyst system of claim 1, wherein the transition metal or transition metal precursor is chromium or chromium precursor. 8. The ethylene according to claim 7, wherein the chromium or chromium precursor is selected from the group consisting of chromium (III) acetylacetonoate, chromium trichloride tristetrahytrofuran and chromium (III) 2-ethylhexanoate. Trimerization catalyst system. 9. The ethylene trimerization catalyst system according to claim 1, wherein the promoter is methylaluminoxane (MAO) or ethylaluminoxane (EAO). 10. Method for producing 1-hexene, characterized in that the ethylene trimerization using the ethylene trimerization catalyst system according to any one of claims 1, 7 and 8.

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