WO2017099394A1

WO2017099394A1 - Ligand compound, organic chromium compound, catalyst system for polyethylene polymerization, and method for preparing polyethylene using same

Info

Publication number: WO2017099394A1
Application number: PCT/KR2016/013650
Authority: WO
Inventors: 박진영; 이용호; 이기수; 신은지; 사석필; 임슬기; 홍윤기
Original assignee: 주식회사 엘지화학
Priority date: 2015-12-09
Filing date: 2016-11-24
Publication date: 2017-06-15
Also published as: KR20170068171A

Abstract

The present invention relates to a ligand compound, an organic chromium compound, a catalyst system for polyethylene polymerization, and a method for preparing polyethylene using the same. The catalyst system according to the present invention has excellent catalytic activity and enables efficient production of polyethylene having a relatively narrow molecular weight distribution.

Description

【Specification】

[Name of invention]

Ligand compound, organic crum compound, catalyst system for polyethylene polymerization, and method for producing polyethylene using the same

Technical Field

Cross Citation with Related Application (s)

This application claims the benefit of priority over Korean Patent Application No. 10-2015-0175064 filed Dec. 9, 2015, and all content disclosed in the documents of that Korean Patent Application is incorporated as part of this specification. The present invention relates to a ligand compound, an organic chromium compound, a system for polyethylene polymerization comprising the ligand compound or an organic crum compound, and a method for producing polyethylene using the same.

[Background technology]

Linear alpha-olefins are used as detergents, lubricants, plasticizers, etc. In particular, linear low-density polyethylene (LLDPE) is used as a comonomer for controlling the density of polymers. Conventional processes for the production of LLDPE include a mixture of alpha-olefins such as 1-nuxene and 1-octene to control the density by forming a branch in the polymer backbone with ethylene. Copolymerization with the monomer was made.

Therefore, there is a problem that the price of the comonomer takes a large part of the manufacturing cost for the production of LLDPE having a high comonomer content. In order to solve this problem, various attempts have been made.

In addition, since alpha-olefins have different types of market or market size, the technology to selectively produce specific olephine is of great commercial importance. Recently, 1-hexene through selective ethylene oligomerization has been used. Or research on chromium catalyst technology to produce 1-octene with high selectivity A lot is done.

These linear alpha-olefins were produced primarily through the Shell Higher Olefin Process. However, the method Schultz-Flory according to the distribution of varying lengths of alpha-olefins, that is, the eu alpha olefin in the liquid form due to oligomerization banung of ethylene is mainly generated, to obtain a polyethylene additional separation ⁱ and the polymerization process There was a hassle to go through again.

[Content of invention]

[Problem to solve]

The present invention is directed to providing novel ligand compounds which can exhibit high catalytic activity in reactions under ethylene conditions and, in particular, enable the polymerization of polyethylene with high selectivity.

The present invention is also to provide a novel organic chromium compound which can exhibit high catalytic activity in reaction under ethylene conditions and enables polymerization of polyethylene with high selectivity.

In addition, the present invention is to provide a catalyst system for polyethylene polymerization comprising the ligand compound or an organic chromium compound.

The present invention also provides a method for producing polyethylene using the catalyst system.

[Measures of problem]

The present invention provides a ligand compound represented by the following formula (1).

[Formula 1]

^ 一 R5

In Chemical Formula 1 N is nitrogen atom, P is phosphorus atom, S is sulfur atom,

L is a hydrocarbylene having 2 to 20 carbon atoms connecting Ν and ^' S, and the shortest distance connecting Ν and S is 2 to 6 carbon atoms,

R1 to R4 are each independently, identically or differently, a hydrocarbyl group or heterohydrocarbyl group having 1 to 20 carbon atoms;

R <5> is a substituted or unsubstituted C1-C10 alkyl group and a substituted or unsubstituted C6-C15 aryl group.

The present invention also provides an organic cream compound comprising chromium (Cr) in which the ligand compound is coordinated.

In addition, the present invention comprises: i) a crum source, said ligand compound, and a promoter; Or ii) a catalyst system for polyethylene polymerization, comprising the organic chromium compound and a promoter.

The present invention also provides a process for producing polyethylene, comprising the step of polymerizing reaction of ethylene in the presence of the catalyst system to form polyethylene. .

【Effects of the Invention】

The polymerization catalyst system according to the present invention has a good catalytic activity in reaction under ethylene conditions, but also has a very high selectivity to polyethylene, and in particular, it is possible to efficiently produce solid polyethylene.

[Brief Description of Drawings]

Figure 1 is a photograph observing the appearance of the polyethylene produced by the present application examples and comparative examples.

[Specific contents to carry out invention]

Hereinafter, a ligand compound, an organic crucible compound, a catalyst system for polyethylene polymerization, and a method for producing polyethylene using the same according to embodiments of the present invention will be described in more detail.

Prior to this, the terminology used herein is merely illustrative. It is used to describe the embodiments, but is not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, terms such as "comprise", "include" or "have" are intended to indicate that there is a feature, a number, a step, a component, or a combination thereof, and one or more other features It should be understood that it does not exclude in advance the possibility of the presence or addition of similarities, steps, components, or combinations thereof.

As the invention allows for various changes and numerous modifications, particular embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to a particular disclosed form, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

In addition, the term 'catalyst system' throughout this specification refers to a three component comprising a crum source, a ligand compound and a promoter, or alternatively, two components of an organic chromium compound and a promoter are simultaneously or in any order. It means the state which can be obtained with an active catalyst composition. Three or two components of the catalyst system may be added in the presence or absence of a solvent and monomer, and may be used in a supported or unsupported state.

In the present specification, the hydrocarbyl group means a monovalent group formed by removing one hydrogen atom from a hydrocarbon, and the heterohydrocarbyl group is formed while one hydrogen atom is removed from a hydrocarbon including a hetero atom.

It refers to a monovalent group, and hydrocarbylene means a divalent linking group formed by removing two hydrogen atoms from a hydrocarbon.

And, in each functional group, the functional group substituted means a state in which one or more other hydrogen atoms are further removed from the hydrocarbon and another functional group or hetero element is substituted. According to one aspect of the present invention, there is provided a ligand compound represented by the formula (1).

[Formula 1]

In Chemical Formula i,

N is a nitrogen atom, Ρ is a phosphorus atom, S is a sulfur atom,

L is a hydrocarbylene having 2 to 20 carbon atoms connecting Ν and S, and the shortest distance connecting Ν and S has 2 to 6 carbon atoms,

R <5> is a substituted or unsubstituted C1-C10 alkyl group and a substituted or unsubstituted C6-C15 aryl group. Conventional aniline based ΡΝΡ-based transition metal catalysts are mainly used for the production of alpha-olefins using ethylene, and the reaction of oligomerization proceeds mainly in reaction under ethylene conditions, and thus, in the form of liquid alpha-olefins, specifically, in liquid form. High selectivity for 1-nuxene or 1-octene. This is known to be due to the increased selectivity for specific lengths of alpha-olefins through the transition state of metalacycles in the ligomerization reaction of ethylene.

However, as a result of the continuous experiments of the present inventors, when the ligand compound of the present invention is applied to the catalyst system for polyethylene polymerization, it shows excellent catalytic activity and selectivity to polyethylene, particularly, compared with the conventional PNP catalyst. In this case, it was confirmed that even under the same reaction conditions, the selectivity to solid polyethylene was very high, thereby enabling the production of more efficient polyethylene.

According to one embodiment of the invention, the ligand compound includes a diphosphino aminyl moiety in the molecule, the nitrogen of the aminyl moiety is a substituent containing a sulfur (S) atom through a hydrocarbylene linker on Connected.

These structural features and the electronic effects of sulfur atoms inhibit the reductive elimination step in conventional olefin oligomerization reaction mechanisms, grow ethylene into longer chains, and increase the selectivity of polyethylene. This will further reduce the amount of other by-products.

The ligand compound described above may be applied to a polyethylene polymerization catalyst system to exhibit high polymerization reaction activity. For example, the ligand compound may have high selectivity for solid polyethylene having a weight average molecular weight of about 5,000 g / mol to about 900,000 g / md. Can be represented. However, the weight average molecular weight range of such polyethylene may vary depending on the specific conditions of the ethylene polymerization reaction.

In addition, the amount of other isomers or by-products that have a great influence on the product in the polymerization reaction can be greatly reduced, and since the selectivity to homo polyethylene is about 100%, the morphology is formed uniformly. In comparison with the process of preparing polyethylene through the reaction of polymerization after preparing ethylene oligomer, it is advantageous in terms of cost and quality of the produced polyethylene. In particular, the selectivity to the solid polyethylene is very high, the concentration of the liquid alpha olefin, that is, the ethylene oligomer, which can participate in the reaction as a comonomer in the reaction vessel is low, and thus fouling effects that may occur in the reactor. Since side effects can be effectively prevented, it is possible to produce high quality solid polyethylene.

In Formula 1, R1 to R4 are each independently, identically or differently, a hydrocarbyl group or a heterohydrocarbyl group.

As a non-limiting example, R1 to R4 are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms substituted or unsubstituted It may be a substituted or unsubstituted arylalkyl group having 7 to 15 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms. Here, the alkyl group, At least one hydrogen contained in a cycloalkyl group, an aryl group, an arylalkyl group, and an alkoxy group may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, or a cyano group.

Preferably, R1 to R4 are each independently methyl, ethyl, propyl, propenyl, propynyl, butyl, cyclohexyl, 2-methylcyclohexyl Omethylcyclohexyl),

2-ethylcyclohexyl,

2-isopropylcyclohexyl, benzyl, phenyl, rylyl (tolyl), xylyl (xylyl), o-methylphenyl, o-ethylphenyl ), 0-isopropylphenyl, ot-butylphenyl,

0-methoxyphenyl, o-isopropoxyphenyl, m-methylphenyl, m-ethylphenyl, m-isopropylphenyl (m- isopropylphenyl), mt-butylphenyl, m-methoxyphenyl, m-isopropoxyphenyl (o-is is propoxyphenyl), P-methylphenyl, p-ethyl Phenyl (p-ethylphenyl), p-isopropylphenyl, pt-butylphenyl, p-methoxyphenyl, p-isopropoxyphenyl, p-isopropoxyphenyl, Cumyl, mesityl, biphenyl, naphthyl, anthracenyl, methoxy, ethoxy, phenoxy, ryloxy ( tolyloxy, dimethylamino, thiomethyl, or trimethylsilyl groups.

R 5 is a substituent linked to a diphosphinoaminyl moiety through a sulfur atom and a linker L, which may be an alkyl group having 1 to 10 carbon atoms, an aryl group having ⁶ to 15 carbon atoms, and in the case of an alkyl group, straight or branched chain. The alkyl group or the aryl group may be substituted with another alkyl group, an aryl group or a functional group containing a hetero atom such as nitrogen, oxygen, phosphorus, sulfur, silicon, or the like.

The R5 may be connected to a sulfur atom through the above-described structure to change the chemical state of the diphosphino aminyl moiety, and further, through the three-dimensional structure, a non-covalent electron pair of the sulfur atom may be directly coordinated to the crum atom. It may be. And, L is connecting the nitrogen atom and sulfur atom of the PNP ligand It is a linker, It is a C2-C20 hydrocarbylene, The carbon number of the shortest distance which connects N and S is 2-6. Preferably, L may be substituted or unsubstituted alkylene having 2 to 20 carbon atoms, or substituted or unsubstituted arylene having 6 to 20 carbon atoms. Particularly in the case of arylene, the nitrogen atom and the sulfur atom are connected to the ortho position. It may be advantageous in terms of steric structure and electron density. According to another aspect of the invention, there is provided an organic chromium compound comprising a credential (Cr) coordinated with the compound represented by the following formula (1).

[Formula 1]

S ^{* ~ * ~} R5

One

In Chemical Formula 1,

N is nitrogen atom, Ρ is phosphorus atom, S is sulfur atom,

L is a hydrocarbylene having 2 to 20 carbon atoms connecting Ν and S, and the shortest distance connecting Ν and S is 2 to 6 carbon atoms,

R1 to R4 each independently, same or different, have 1 to C

20 hydrocarbyl group or heterohydrocarbyl group;

Details of Formula 1 are as described in the Ligand Compound section.

The organic crum compound is a complex compound of the aforementioned ligand compound, and may have a form in which chromium of a chromium source has a covalent bond formed by a non-covalent electron pair of a nitrogen atom of a group represented by Formula 1. These organic kink compounds have been applied to a catalyst system for the polymerization of ethylene to provide excellent catalytic activity and high resistance to solid polyethylene. It may indicate selectivity.

In addition, according to an embodiment of the present invention, it may be preferable that the organic crum compound has a form in which at least one non-covalent electron pair among N, P, and S in the ligand compound is coordinated with a chromium atom. That is, in addition to the phosphorus atom or the nitrogen atom of the diphosphino aminyl moiety, the sulfur atom of the substituent may provide a non-covalent electron pair to the chromium atom, as described above. In particular, three pairs of non-covalent electron pairs are coordinated. Tridentated forms may be preferred. On the other hand, according to another aspect of the invention, i) comprises a chromium source, the ligand compound, and a promoter; Or ii) a catalyst system for polyethylene polymerization, comprising the organic crum compound and a promoter.

That is, according to one embodiment of the invention, the catalyst system for polyethylene polymerization comprises: i) a three-component catalyst system comprising a chromium source, a ligand compound and a promoter as described above, or ii) an organic crum compound and a promoter as described above. It may be a two-component catalyst system.

Specific descriptions and examples of the ligand compound and the organic crum compound are replaced with the above description.

In the catalyst system, the ctom source is an organic or inorganic crumky compound in which the oxidation state of chromium is 0 to 6, for example chromium metal, or a compound in which any organic or inorganic radical is bonded to chromium. Here, the organic radical may be an alkyl, alkoxy, ester, ketone, amido, carboxylate radical or the like having 1 to 20 carbon atoms per radical, and the inorganic radical may be a halide, sulfate, oxide or the like.

Preferably, the chromium source is a compound that can exhibit high activity in the polymerization reaction of ethylene and is easy to use and obtain, such as chromium (III) acetylacetonate, chromium (III) chloride tetrahydrofuran, chromium (III) 2 Ethylnucleosanate, chromium (III) acetate, chromium (III) butyrate, chromium (III) pentanoate, chromium (III) laurate, chromium (III) tris (2,2,6,6-tetramethyl) 3.5-heptanedionate), and chromium (III) stearate. And, preferably, the promoter is an organometallic compound containing a Group 13 metal, and can be applied without particular limitation as long as it can be generally used when polymerizing ethylene under a catalyst of a transition metal compound.

For example, the promoter may be at least one compound selected from the group consisting of compounds represented by Formulas 2 to 4 below:

[Formula 2]

-[Al (Rx) -0] _c -in Formula 2, AIII is aluminum,

Rx is the same as or different from each other, and each independently a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen, c is an integer of 2 or more,

[Formula 3]

D (Ry) ₃

In Chemical Formula 3, D is aluminum or boron, Ry is C1-20 hydrocarbyl or halogen substituted by C1-20 carbonyl,

[Formula ⁴ ]

[LH] ⁺ [Q (E) ₄ ] ^"

In Chemical Formula 4,

L is a neutral Lewis base, [LH] ⁺ is Bronsted acid, Q is boron or aluminum in the +3 type oxidation state, each E is independently at least one hydrogen atom is halogen, a hydrocarbyl having 1 to 20 carbon atoms, An aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with an alkoxy functional group or a phenoxy functional group. .

According to one embodiment, the compound represented by Formula 2 may be alkyl aluminoxane, such as methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane.

In addition, according to one embodiment, the compound represented by Formula 3 is trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, Dimethylisobutylaluminum, dimethylethylaluminum, diethylchloroaluminum triisopropylaluminum, tributylaluminum, tricyclopentylaluminum tripentylaluminum, triisopentylaluminum, trinuclear silaluminum ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum Tri-P-allyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum-specific trimethyl boron, triethyl boron, triisobutyl boron ,. Tripropylboron tributylboron and the like.

According to one embodiment, the compound represented by Formula 4 is triethylammonium tetraphenylboron, tributylammonium tetra.phenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium Umtetra (P-lryl) boron ， Tripropylammoniumtetra (P-lryl) boron, Triethylammoniumtetra (ο, ρ-dimethylphenyl) boron ，

Trimethylammonium tetra (ο, ρ-dimethylphenyl) boron ，

Tributylammonium tetra (Ρ-trifluoromethylphenyl) borone ，

Trimethylammonium tetra (Ρ-trifluoromethylphenyl) boron,

Tributylammonium tetrapentafluorophenylborone ，

Ν, Ν-diethylanilinium tetraphenyl boron, Ν, _Ν -diethylanilinium tetraphenylboron, Ν, _Ν -diethylanilinium tetrapentafluorophenylboron,

Diethylammonium tetrapentafluorophenylboron,

Triphenyl phosphonium tetraphenyl boron, trimethyl phosphonium tetraphenyl boron, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetraphenyl aluminum,

Tripropyl ammonium tetraphenylaluminum ，

Trimethylammonium tetra (Ρ-ryll) aluminum,

Tripropylammonium tetra (Ρ-ryl) aluminum,

Triethylammonium tetra (ο, ρ-dimethylphenyl) aluminum,

Tributylammonium tetra (Ρ-trifluoromethylphenyl) aluminum,

Trimethylammonium Tetra (Ρ-trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenylaluminum, Ν, Ν-diethylanilinium tetraphenylaluminum, Ν, Ν-diethylanilinium tetraphenylaluminum , N, _N - diethyl phenyl aluminum shall not, in Titanium tetra-penta _flow.

Diethylammonium tetrapentafluorophenylaluminum,

Triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, triphenylcarbonium tetraphenylboron, triphenylcarbonium tetraphenylaluminum, triphenylcarbonium tetra (Ρ-trifluoromethylphenyl) boron,

Triphenylcarbonium tetrapentafluorophenylboron and the like.

In addition, as a non-limiting example, the promoter may be an organoaluminum compound, an organoboron compound, an organomagnesium compound, an organozinc compound, an organolithium compound, or a combination thereof. According to one embodiment, the promoter is preferably an organoaluminum compound, more preferably trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum (triisobutyl aluminum), ethylaluminum sesquichloride, diethylaluminum chloride, ethyl aluminum dichloride, methylaluminoxane, and modified methylaluminoxane It may be one or more compounds selected from the group consisting of

On the other hand, the content ratio of the components constituting the catalyst system may be determined in consideration of the catalytic activity and the selectivity to polyethylene. According to one embodiment, in the three component catalyst system, the molar ratio of diphosphino aminyl moiety: chromium source: cocatalyst of the ligand compound is about 1: 1: 1 to 10: 1: 10,000, or about 1: 1 It is advantageous to adjust from: 100 to 5: 1: 3,000. And, in the case of the two-component catalyst system, the molar ratio of diphosphino aminyl residue: cocatalyst of the organic chromium compound is from 1: 1 to 1: 10,000, or from 1: 1 to 1: 5,000, or from 1: 1 to 1: 1. It is advantageous to adjust to 3,000.

The components constituting the catalyst system can then be added simultaneously or in any order, in the presence or absence of suitable solvents and monomers, to act as an active catalyst system. At this time, suitable solvents include heptane, toluene, cyclonucleic acid, methylcyclonucleic acid, 1-nuxene, 1-octene, diethyl ether, Tetrahydrofuran, acetonitrile, ^{dichloromethane,.} Chloroform, chlorobenzene, methanol, acetone and the like can be used.

In addition, according to one embodiment of the invention, the catalyst system may further comprise a carrier. That is, the ligand compound of Formula 1 may be applied to the ethylene polymerization reaction in the form supported on the carrier. The carrier may be a metal, a metal salt, a metal oxide, or the like applied to a conventional supported catalyst. As a non-limiting example, the carrier may be silica, silica-alumina, silica-magnesia, and the like, and oxides, carbonates, sulfates, nitrates of metals such as Na ₂ 0, K ₂ C0 ₃ , BaS0 ₄ , Mg (N0 ₃ ) _2, and the like. It may include ingredients. On the other hand, according to another aspect of the present invention, in the presence of the catalyst system described above, by proceeding the polymerization reaction of ethylene, to form a polyethylene; provides a method for producing polyethylene comprising a.

The process for producing polyethylene according to the invention can be carried out by applying conventional equipment and contacting techniques with the above-mentioned catalyst system with ethylene as raw material. As a non-limiting example, the polymerization reaction of ethylene may be a homogeneous liquid reaction in the presence or absence of an inert solvent, or a slurry reaction in which the catalyst system is partially or completely insoluble, or the product polyethylene is the main medium. Bulk reaction, gas phase reaction, or the like. And, the polymerization reaction of the ethylene can be carried out under an inert solvent. As a non-limiting example, the inert solvent may be benzene, toluene, xylene, cumene, chlorobenzene, dichlorobenzene, heptane, cyclonucleic acid, methylcyclonucleic acid, methylcyclopentane, η-nucleic acid, 1-nuxene, 1-octene, etc. have.

And, the polymerization reaction of the ethylene may be performed at a temperature of about 0 to about 200 ^° C, or about 0 to about 150 ^° C, or about 30 to about 100 ^° C, or about 50 to about 100 ^° C. In addition, the reaction may be performed under a pressure of about 15 to about 3000 psig, or about 15 to about 1500 psig, or about 15 to about 1000 psig. Hereinafter, through the specific examples of the invention, the operation and effects of the invention It will be described in detail. However, these embodiments are only presented as an example of the invention, whereby the scope of the invention is not determined.

All reactions were performed under argon using the Schlenk technique or glove box. The synthesized ligand was analyzed by 1H (500 MHz) and ³¹ P (202MHz) NMR spectra using a Varian 500 MHz spectrometer. Shifts were expressed as ρρϊ in downfield from TMS with residual solvent peak as reference. · Phosphorous probes were calibrated with aqueous 0 ₄ .

Synthesis of (Ph) ₂ P (h) ₂

10 mm of 2- (Phenylthio) aniline was weighed in a dried Schlenk flask, vacuum dried for 1 hour or longer, replaced with Ar, and 80 ml of dichloromethane was added under an Ar atmosphere.

Under water bath conditions, Triethylamine 30mm and Chlorodiphenylphosphine 20mm were slowly added dropwise under stirring, and it was confirmed that the slurry became a slurry as soon as Chlorodiphenylphosphine was added dropwise.

The temperature was slowly raised to room temperature, and the mixture was stirred at room temperature for 6 hours. After the solvent was removed in vacuo, it was dissolved in THF and triethylammonium chloride salt was removed. The solvent was removed from the filtrate to obtain a compound in an off-white solid state.

1H NMR (500MHz, CDC1 ₃ ) 7.80-6.62 (30H, m)

31 P NMR (202MHz, CDC1 ₃ ) 62.3 (s) Comparative Synthesis Example 1

Synthesis of 4-Amino-l, 3, 5-trimethyl- ¹ H-pyrazole 10mm in a dried Schlenk flask was weighed, vacuum-dried for 1 hour or more, substituted with Ar, and 80ml of dichloromethane was added under Ar atmosphere.

Under water bath conditions, triethylamine 80 mm and Chlorodiphenylphosphine 20 mm were slowly added dropwise under stirring, and it was confirmed that as soon as Chlorodiphenylphosphine was added dropwise, it became a slurry state.

The temperature was slowly raised to room temperature, and the mixture was stirred at room temperature for 6 hours. After the solvent was removed in vacuo, it was dissolved in THF and triethylammonium chloride salt was removed. The solvent was removed from the filtrate to obtain a white solid compound.

JH NMR (500MHz, CDC1 ₃ ) 7.46-7.24 (20H, m), 3.51 (3H, s), 1.14 (3H, s)

³¹ P NMR (202MHz, CDC1 ₃ ) 66.12 (s)

Comparative Synthesis Example 2

P (Ph) ₂

Synthesis of (Ph) ₂ ^\ p (Ph) ₂

Weigh 1min of 2-Aminobenzylamine in the dried Schlenk flask, and 1 hour After vacuum drying, the mixture was replaced with Ar, and 50 ml of dichloromethane was added under an Ar atmosphere.

Under water bath, under stirring, Triethylamine 80mm and Chlorodiphenylphosphine 20mm were slowly added dropwise, and the light red colored oxime became slurry as soon as Chlorodiphenylphosphine was added.

MR NMR (500MHz, CDC1 ₃ ) 11.74 (2H, s), 7.67-6.50 (44H, m)

Preparation of ^3I P NMR (202MHz, CDC1 ₃ ) 60.67 (s) catalyst system and progress of ethylene bed reaction

Example 1 and Comparative Examples 1 and 2

In an argon gas atmosphere, chromium (III) acetylacetonate (17.5 mg, 0.05 mmol) and ligand compounds (0.055 mmol) according to Synthesis Example 1 and Comparative Synthesis Examples 1 and 2 were placed in a flask, followed by 100 ml of cyclo The nucleic acid was added and stirred to prepare a catalyst solution of 0.5 mM (Cr basis).

Parr reaction vessels of 600 ml capacity were prepared and vacuumed at 180 ^° C for 2 hours, after which the interior was replaced with argon and the temperature was lowered to 60 ^° C. Thereafter, 140 g of metallophthalic acid and 3 mmol (Al) of MAO were injected, and 5 ml (2.5 μηαοΐ Cr) of 0.5 mM of the catalyst solution was injected. The valve of the ethylene line set to 60 bar was opened to fill the inside of the reaction vessel with ethylene, and then adjusted to heat at 60 ^° C., followed by reaction for 15 minutes at 500 rpm.

After completion of the reaction, 2 ml of the liquid portion of the reaction was taken, and the distribution of the liquid product was analyzed by GC. In addition, the remaining reaction solution was quenched with ethanol / HCl (10 vol% of aqueous) solution and filtered to analyze the amount of solids. The results of the Examples and Comparative Examples are summarized in Table 1 below. Table 1

Referring to Table 1, the catalyst used in the examples of the present application, it can be seen that the catalytic activity is very high compared to the comparative example, it can be confirmed that can overwhelmingly polymerize a large amount of polyethylene close to about 30 times.

In addition, the selectivity of the polyethylene in the ^ property is about 100%, it can be seen that very high compared to 4.4% of Comparative Example 1, 15.3% of Comparative Example 2.

The appearance of the polyethylene prepared in Examples and Comparative Example 1 is shown in FIG.

Referring to Figure 1, in the case of the polyethylene produced by the embodiment of the present application, it can be seen that it is formed as a solid in a uniform powder form, in the case of Comparative Example 1, that it is formed as an irregular and non-uniform solid You can check it.

On the other hand, in the case of Comparative Example 1 and Comparative Example 2, after the continuous process of olefin oligomerization reaction, a solid product (solid alpha-olefin or solid polyethylene) remaining in the reaction vessel was obtained, and together with the polyethylene obtained in Example 1 The average molecular weight (Mn), the weight average molecular weight (Mw) and the molecular weight distribution (PDI) were calculated | required using the gel permeation chromatography (GPC), and it was put together in Table 2.

Table 2

Referring to Table 2, it can be confirmed that the Examples of the present application have a narrower molecular weight distribution than the Comparative Example. That is, in the case of the comparative example, it can be seen that a variety of solid polyethylene having a wide molecular weight distribution is produced as a by-product of the olefin oligomerization reaction, in the case of the embodiment, it can be confirmed that a polyethylene having a relatively narrow molecular weight distribution value is obtained.

Claims

Claims Claim 1 Ligand compound represented by the following general formula (1):

[Formula 1]

Rlk

R2 R3

In Chemical Formula 1,

N is a nitrogen atom, Ρ is a phosphorus atom, S is a sulfur atom,

[Claim 2]

The method of claim 1,

R1 to R4 are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms substituted or unsubstituted, substituted or unsubstituted A arylalkyl group having 7 to 15 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms.

[Claim 3]

An organic creme compound comprising a creme (Cr) coordinated with a ligand compound represented by Formula 1 below: [Formula 1]

In Chemical Formula l,

N is a nitrogen atom, Ρ is a phosphorus atom, S is a sulfur atom,

R1 to R4 are each independently the same or differently a hydrocarbyl group or heterohydrocarbyl group having 1 to 20 carbon atoms;

[Claim 4]

The method of claim 3, wherein

The organic chromium compound is an organic chromium compound in the form of a ligand compound of Formula 1 wherein at least one non-covalent electron pair among N, P, and S is coordinated with a creme atom.

[Claim 5]

i) a chromium source, the ligand compound of claim 1, and a promoter

Include;

or

ii) comprising the organic chromium compound of claim 3 and a promoter; Catalyst system for polyethylene polymerization. [Claim 6] The method of claim 5, wherein:

The chromium source is chromium (III) acetylacetonate, chromium (III) chloride tetrahydrofuran, chromium (III) 2-ethylnucleoanoate, chromium (III) acetate, chromium (III) butyrate, chromium (III) pentano 8, chromium (III) laurate, chromium (III) tris (2,2,6,

6-tetramethyl-3.5-heptanedionate), and chromium (ΠΙ) stearate comprising at least one member selected from the group consisting of.

[Claim 7]

The method of claim 5, wherein.

The promoter is trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, ethylaluminum sesquichloride, diethylaluminum Catalyst system for polyethylene polymerization, comprising one or more selected from the group consisting of diethylaluminum chloride, ethyl aluminum dichloride, methylaluminoxane, and modified methylaluminoxane . [Claim 8]

In the presence of a catalyst system according to claim 5, comprising the step of polymerizing reaction of ethylene to form polyethylene.