JP2002503733A - Catalyst compound containing β-diamine anionic ligand and method for polymerizing olefin - Google Patents

Abstract

The present invention relates to catalyst systems, processes for the preparation of such catalysts, intermediates for such catalysts, and methods for polymerizing olefins using such catalysts, wherein such catalysts have the formula It comprises a compound of formula (I) and optionally a compound of formula (a). Wherein R and R ′ are each a hydrogen atom, or a substituted or unsubstituted, branched or unbranched hydrocarbyl or organosilyl group, and R ¹ , R ² and R ³ are each a hydrogen atom, or A substituted or unsubstituted, branched or unbranched hydrocarbyl group, M is a IIIB, IVB, VB, VIIB or VIII transition metal, and T is each a monovalent anionic ligand; For example, a hydrogen atom or a substituted or unsubstituted hydrocarbyl, halogeno, aryloxide, arylorganosilyl, alkylorganosilyl, amide, arylamide, phosphide or arylphosphide group, or two T groups are jointly alkylidene Or a cyclometallated hydrocarbyl bidentate ligand, wherein L is a sigma-donating stabilizing ligand, respectively. And optionally present X is a relatively weakly coordinated anion, a = 0-4, b = 0-4, and a + b ≦ 4. Embedded image

Description

DETAILED DESCRIPTION OF THE INVENTION

TECHNICAL FIELD [0001] The present invention relates to catalyst systems, methods for producing such catalysts, and methods for polymerizing olefins using such catalysts.

BACKGROUND OF THE INVENTION Olefin polymers are useful as plastics, moldings, films, etc., for packaging materials, as well as elastomers for moldings, various industrial belts, tires, adhesives and other uses. . It is known in the art that the structure of an olefin polymer, and therefore its properties and utility, depends greatly on the catalyst used to synthesize the polymer. Thus, in recent years, as the possible uses of polymers have changed and developed, new and additional catalyst systems and improved polymerization processes using such catalysts have been required.

DISCLOSURE OF THE INVENTION According to the present invention, there is provided a novel catalyst system for olefin polymerization, which comprises a transition metal complex having a β-diiminate bidentate ligand. According to the present invention, there is also provided a novel catalyst compound component for olefin polymerization, wherein the compound has the formula (I):

Embedded image Wherein R and R ′ are each a hydrogen atom, or a substituted or unsubstituted, branched or unbranched hydrocarbyl or organosilyl group; R ¹ , R ² and R ³ are each a hydrogen atom, Or a substituted or unsubstituted, branched or unbranched hydrocarbyl group; M is a Group IIIB, IVB, VB, VIB, VIIB, or VIII transition metal; and T is a monovalent anionic moiety. A ligand such as a hydrogen atom or a substituted or unsubstituted hydrocarbyl, halogeno, aryloxide, arylorganosilyl, alkylorganosilyl, amide, arylamide, phosphide or arylphosphide group, or two T groups. L is jointly a ligand such as an alkylidene or cyclometallated hydrocarbyl group; Either a donor stabilizing ligand, or one L and one T
Is jointly a second β-diiminate of the formula (II) (below); optionally present X is a relatively weakly coordinated anion; a is an integer from 0 to 4, b is 0 A + b ≦ 4. ] The catalyst compound component which is a compound shown by these is provided.

Further, according to the present invention, there is provided a novel method for polymerizing olefins. The process comprises the steps of reacting one or more heterogeneous catalysts in the presence of a homogeneous catalyst comprising a catalyst of the formula (I) or a heterogeneous catalyst comprising a catalyst of the formula (I) and one or more auxiliary catalysts. It consists of polymerizing further olefins.

In addition, the present invention provides a compound containing a transition metal of Group IIIB, Group IVB, Group VB, Group VIB, Group VIIB or Group VIII including a β-diiminate ligand represented by the following formula (II): The present invention provides a novel method for producing a catalyst component represented by the formula (I) by contacting with a compound, particularly a compound represented by the following formula (III).

[0006]

Embedded image

Embedded image (Wherein, R, R ′, R ¹ , R ² and R ³ are as defined above, and m includes a group easily substituted by a transition metal, for example, a hydrogen atom or a Group IA or IIA metal. Represents a group.)

As used herein, certain terms are used to define certain chemical groups and compounds. Such terms are defined below. “Alkyl metal” or “metal alkyl” refers to a compound having an alkyl group bonded directly to a metal. For example, an alkyl metal (or metal alkyl) includes an aluminum alkyl (or aluminum alkyl).

[0008] "Groups IA, IIA, IIB, IIIA, IIIB, IVB, VB, VIB, VI
Group IB or VIII ”means the Periodic Table of the Elements (CRC Handbook of Chemistry and Physics).
, 78th edition (1997-1998). For example, Group IVB includes titanium, zirconium, and the like, and Group VIII includes palladium, platinum, cobalt, and the like.

“Hydrocarbyl” means a monovalent group containing only carbon and hydrogen. Unless otherwise stated, hydrocarbyl as used herein is preferably from 1 to about 30
Containing carbon atoms. The “linear α-olefin” is an olefin represented by the following formula in which R ¹⁰ represents a hydrogen atom or n-alkyl. Unless otherwise stated, linear α as used herein
The olefin preferably contains 2 to about 12 carbon atoms. “Olefin” is a compound represented by the formula: CH ₂ ＣＨCHR ₁₀ (where R ¹⁰ represents a hydrogen atom or n-alkyl or branched alkyl, preferably a hydrogen atom or n-alkyl). It is.

“Organosilyl” means a monovalent group containing at least one carbon atom in a silicon bond. One example is trimethylsilylmethyl. "Polymerization" refers to a method of making polymers, copolymers, terpolymers, and the like, generally having a degree of polymerization of at least about 20. However, the method is also useful for producing oligomers with a lower degree of polymerization.

“Saturated hydrocarbyl” means a hydrocarbyl group that has no double or triple bonds. Examples of such groups include alkyl and cycloalkyl. "Substituted hydrocarbyl" refers to a hydrocarbyl group having one or more substituents.

A “transition metal” is generally a group IIIB, IVB, VB, VIB, VIIB or
Group VIII transition metal. Unless stated otherwise, the transition metals used herein are preferably Group IVB, VB or VIB transition metals. "Unsaturated hydrocarbyl" refers to a hydrocarbyl group having one or more double or triple bonds. Examples of such groups are olefin groups, acetylene groups or aromatic groups.

The present invention provides a homogeneous transition metal catalyst complexed by a β-diiminate bidentate ligand or a catalyst system comprising at least one such transition metal catalyst and one or more cocatalysts. The present invention relates to a method and a catalyst for polymerizing an olefin.

The β-diiminate ligand has the following formula (II):

Embedded image Wherein R, R ′, R ¹ , R ² and R ³ are as defined above, wherein the transition metal has a ligand bonded thereto. May be replaced by or attached to the olefin.

Reaction Scheme 1 below details one method of synthesizing a β-diiminate precursor compound corresponding to the β-diiminate monoanionic ligand of formula (II). This synthesis reaction is described in SG McGeachin, Canadian J. of Chem. 46, 1903-1912.
P. (1968) and T. Potesil and H. Potesilova, J. of Chromatogr., 31.
2, pp. 387-393 (1984). From this series of transformations, it is understood that β-diimine compounds having different groups on each nitrogen atom can be easily prepared by using two different substituted amines in the reaction route. Following the well-known abbreviation "acac" for the acetylacetonato group, the abbreviation "nacnac"
"Is used to represent a 2,4-pentanediiminato group represented by the formula (II). For example, the diimine structure bridged by hydrogen or lithium in the last two steps of Reaction Scheme 1 can be represented as nacnacH or nacnacLi, respectively. As used herein, nacnac further includes a prefix indicating the type of group present at the R and R ′ positions, eg, “Me” for a methyl group or “Ph” for a phenyl group (eg, (Ph) (Me) nacnacH or (Ph) ₂ nacnacH).

[0016]

Embedded image Reaction Scheme 1: Synthesis of β-diiminate (R) (R ′) nacnacLi

The catalyst compounds of the present invention use novel β-diimine compounds and the corresponding monoanionic β-diiminate ligands, as well as known precursors for the cationic and anionic portions of the catalyst compound. Can be prepared in various ways. The catalyst compounds of the present invention can be formed in advance or in situ (ie, in a vessel in which the polymerization is performed).

The β-diimine compound of the formula (III) is useful as a precursor of a monoanionic bidentate ligand represented by the formula (II) and reacts with a transition metal compound to form a compound represented by the formula (I) The catalyst compounds shown can be produced. This catalyst compound is useful for olefin polymerization. In a preferred form of the β-diimine compound of the formula (III), the hydrogen or metal-containing group denoted by m includes hydrogen or a Group IA metal, especially lithium, sodium or potassium.

[0019] Transition metal-containing compounds useful for forming such catalyst compounds include Group IIIB having ligands that can be replaced by monoanionic bidentate ligands derived from β-diimine precursor compounds. , IVB, VB, VIB, VIIB or VIII transition metal. Particularly suitable transition metal-containing compounds are those of the formula (I)
And / or a transition metal salt having a ligand in addition to and / or including the ligand represented by L. This ligand is easily replaced by a ligand derived from a diimine precursor compound under conditions that do not adversely affect either the metal compound or its ligand adduct. Transition metal salts include transition metal halides (eg, dichloride, trichloride or tetrachloride, preferably trichloride), transition metal carboxylates (eg, acetate), transition metal alkoxides (eg, methoxide), or transition metal sulfonates (eg, , Triflate or tosylate).

[0020] Typically, these catalysts are synthesized in the presence of a suitable solvent. Suitable solvents include Lewis bases such as ethers, thioethers, amines or nitriles, with diethyl ether and tetrahydrofuran being preferred. In addition, metal alkyls, especially those having a Group IA, IIA or IIIA metal, such as lithium alkyls (eg methyllithium, ethyllithium, n-propyllithium and / or isopropyllithium, n-butyl or t-butyl) Butyllithium), aluminum alkyl, preferably aluminum trialkyl (eg, trimethylaluminum, triethylaluminum, triisobutylaluminum or trioctylaluminum), Grignard reagent and the like are reacted with other reagents to obtain the desired catalyst compound. Alternatively, a compound comprising a β-diiminate ligand, such as a compound of formula (I), is then reacted with such a metal alkyl to obtain the desired catalyst compound, or a compound of formula (I) Can be reacted in situ in the presence of an olefin to give a catalyst having the desired activity.

With respect to the catalyst compound of formula (I), the relatively weakly coordinated anion X
May, if present, be a suitable anion known for the purposes of the present invention.
Suitable anions are often bulky anions, especially anions that localize negative charges.
It is. In the formula (I), X is preferably tetrakis [3,5-bis (trifluoromethyl) phenyl] borate (hereinafter referred to as BArF^-Abbreviation), (phenyl)_FourB^-, (C ₆ H_Five)_FourB^-, (CH_Three) (C₆H_Five)_ThreeB^-, PF₆ ^-, BF_Four ^-, SbF₆ ^-, Trifluorome
Tansulfonate (hereinafter, triflate or OTf^-Abbreviations) and p-toluenesulfonate (hereinafter, tosylate or OTs).^-Abbreviation). Preferred weakly coordinated anions include BArF^-And (C₆H_Five)_FourB^-Is included. Catalyst compounds of the formula (I) in which a weakly coordinated anion is present can be prepared in the presence of a suitable solvent.
Below, a compound of formula (I) having at least one alkyl group is conjugated with a conjugate base of (
About 1 equivalent of a strong acid which is a non-coordinating binding anion (as described for X above)
Can be prepared. Suitable solvents include, for example, methylene chloride, hexane
Including sun, benzene, toluene, chlorobenzene, diethyl ether, etc.
You.

The substituents designated R, R ′, R ¹ , R ² and R ³ should be selected so as not to substantially interfere with or interfere with the particular polymerization reaction for which the catalyst is designed. . Whether a group interferes is determined by one skilled in the art based on the parameters of the method in which the catalyst will be used. For example, in polymerization processes in which an alkyl aluminum compound is used, a catalyst containing an active (relatively acidic) hydrogen atom, such as a hydroxyl or carboxyl group, reacts with the known reaction between the alkyl aluminum compound and such an active hydrogen containing group. Would be undesirable (but if enough "excess" alkylaluminum compound is added to react with such a group,
A polymerization reaction would be possible). However, in very similar polymerization processes where no alkylaluminum compound is present, such active hydrogen-containing groups may be present. An important factor to consider when determining the availability of a compound containing a particular functional group is the effect of the group on the coordination bond of the metal atom, and the side reactions of such groups with other reactants. It is. Thus, of course, the further the functional group is from the metal atom, the less influence it has on, for example, polymerization. If you suspect that a particular functional group at a particular position will affect the reaction, a simple minimal experiment can provide the required answer.

In a preferred example of formula (I), R and R ′ independently represent a hydrogen atom or an alkyl, aryl, alkylaryl, arylorganosilyl or alkylorganosilyl group. Preferably, R and R 'are independently groups having a carbon atom directly attached to the nitrogen having at least two carbon atoms attached thereto, such as isopropyl, phenyl, 2,6-isopropylphenyl, 2,6-dimethyl Represents phenyl, 2,6-diethylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl or 2-t-butylphenyl. R ¹ , R ² and R ³ independently represent a hydrogen atom or a hydrocarbyl group, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen or methyl group. M represents a group IVB, VB or VIB transition metal, preferably chromium, vanadium or titanium. These substituents, which, when present, define preferred examples of compounds of formula (I) are
The same applies to the preferred examples of β-diiminate ligands and β-diiminate compounds represented by formulas (II) and (III), respectively.

Examples of the hydrocarbyl group represented by T in the formula (I) include methyl, ethyl, propyl, butyl, amyl, isoamyl, hexyl, isobutyl, heptyl, octyl, nonyl, decyl, cetyl, and 2-ethylhexyl. , Phenyl and the like, with methyl being preferred. Examples of the halogeno group represented by T include chloro, bromo, fluoro and iodo, with chloro being preferred. Examples of the alkoxide or aryl oxide represented by T include methoxide, ethoxide, phenoxide, and substituted phenoxide. Examples of the amide group represented by T include dimethylamide, diethylamide, methylethylamide, di-t-butylamide, diisopropylamide and the like. Examples of arylamides represented by T include diphenylamide and other substituted phenylamides. The phosphide group represented by T includes diphenyl phosphide, dicyclohexyl phosphide, diethyl phosphide, dimethyl phosphide and the like. Examples of the alkylidene anionic ligands in which two T are put together include methylidene, ethylidene and propylidene.

Each L in the above formula (I) can represent a suitable electron donating ligand. Suitable ligands include those containing atoms with a non-bonded pair of electrons, such as oxygen, nitrogen, phosphorus or sulfur. Non-limiting examples of such ligands include ethers, amines,
Includes phosphines and thioethers. Ethers such as tetrahydrofuran (THF) and amines such as pyridine are preferred, with THP being especially preferred.

In a preferred example of the catalyst compound represented by the formula (I), a and b are independently 0
To 3 (including both ends). More preferably, a and b are independently 0
Or 2 is represented. When Formula (I) represents a mixture of two or more catalyst compounds, a and b represent the average of a and b of those compounds, each being a number from 0 to 4, for example, 1.2 to 1.8. Represents the number of

The polymerization reaction using the catalyst of the present invention can be carried out using the catalyst compound represented by the formula (I) itself (referred to as a homogeneous catalyst system) or together with one or more auxiliary catalysts. The catalyst and cocatalyst may be initially solid or in solution. The olefin and / or olefins may be gas or liquid (including gas dissolved in a solvent). A liquid may or may not be a solvent for any or all of the reactants and / or products. Suitable liquids include alkanes, cycloalkanes, halogenated and cycloalkanes, and ethers. Particularly useful solvents are methylene chloride, hexane, toluene, dichlorobenzene, and benzene.

Cocatalysts useful in the practice of the present invention include IIA, IIB, IIIA and III having at least one alkyl group (preferably an alkyl group having 1 to 8 carbon atoms) bonded to a metal.
Group B metal alkyl. Suitable metal alkyls include dialkyl magnesium, dialkyl zinc, trialkyl borane, triaryl borane and aluminum alkyl. Suitable aluminum alkyls include trialkylaluminums (eg, trimethylaluminum, triethylaluminum, triisobutylaluminum, and trioctylaluminum). Trialkyl aluminum having an alkyl group having 4 or more carbon atoms is preferred. Other aluminum alkyls useful in the practice of the present invention are alkyl aluminum alkoxides (
For example, diethylaluminum ethoxide and ethylaluminum diethoxide, and alkylaluminum halides (eg, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide, diethylaluminum fluoride, ethylaluminum dichloride, ethylaluminum dibromide, ethylaluminum diiodide) , Ethyl aluminum difluoride, and ethyl aluminum sesquichloride). Suitable triarylboranes are those substituted with fluorine (eg, tripentafluorophenylborane)
Is included.

Other suitable aluminum alkyls are those of the formula (R ″ —Al—O) _n (
Cyclic aluminoxane) and aluminoxanes including those represented by the formula R "(R" -Al-O) _n- Al (R ") ₂ (linear). In these formulas, R" is An alkyl group (eg, methyl, isopropyl, butyl, etc.), preferably an alkyl group having more than 2 carbon atoms, more preferably an alkyl group having 3 to 5 carbon atoms, and n is an integer, preferably about 1 to 20; It is an integer. Most preferably, R comprises a methyl or isobutyl group. Mixtures of linear and cyclic aluminoxanes useful in the present invention include, but are not limited to, ethylaluminoxane, isobutylaluminoxane, and methylaluminoxane.

Preferred metal alkyl cocatalysts typically include aluminoxanes and trialkylaluminums. If a cocatalyst is used, the molar ratio of metal alkyl cocatalyst to catalyst should be from about 1: 1 to about 1000: 1. Preferred molar ratios are from about 10: 1 to about 200: 1.

The catalyst system of the present invention can be used in a slurry or gas phase polymerization process. After generating the catalyst, the polymerization reaction is carried out by mixing the monomer and a catalytic amount of the catalyst at a temperature and pressure sufficient to initiate the polymerization reaction. If desired, organic solvents can be used as diluents and to make the material easier to handle. The polymerization reaction is
Depending on the pressure during the reaction, the pressure of the whole monomer, the catalyst used, and its concentration,
The reaction is performed at a temperature of about -100C to about 200C. The temperature is preferably about 20-135
° C. The pressure may be such as to be sufficient to initiate polymerization of the monomer. For example, pressures can range from about atmospheric pressure to about 1000 psig. Typically, a pressure of about 20-800 psig is preferred.

When a catalyst is used in the slurry type method, an inert solvent is used. The solvent should be inert to all other components and products of the reaction and should be stable under the reaction conditions applied. However, such inert organic solvents need not function as solvents for the resulting polymer. Inert organic solvents that can be used include saturated aliphatic hydrocarbons (eg, hexane, heptane, pentane, isopentane, isooctane, purified kerosene, etc.), saturated halogenated alkanes (eg, dichloromethane, chloroform, etc.), saturated alicyclic hydrocarbons (eg, dichloromethane, chloroform, etc.). For example, cyclohexane, cyclopentane, dimethylcyclopentane, etc.), and aromatic hydrocarbons (eg, benzene, toluene, xylene, etc.). Particularly preferred solvents are dichloromethane, toluene, cyclohexane, hexane, benzene and heptane.

When using a catalyst in a gas phase process, the catalyst may be dispersed in a fluid phase (eg, with ethylene). Temperature, pressure and ethylene flow rate are adjusted to maintain acceptable fluidization of the catalyst particles and the resulting polymer particles.

The catalyst of the present invention may be a solid catalyst support (eg, silica gel or other suitable catalyst support that does not adversely affect the performance of the catalyst) (in a sense other than simply added as a solid or in solution). ) Can be used. Supported means that the catalyst can simply be physically located on the surface of the solid support, or that it can be adsorbed, absorbed or placed on the support by other means.

Preferred olefins and cycloolefins for polymerization include at least one or more of the following monomers: ethylene, propylene, 1-butene, cyclopentene, 1-hexene; ethylene, and ethylene and propylene and / or 1-hexene. Mixtures with hexene are more preferred. It is particularly preferred to use only ethylene. Oligomers may be used, in which case comonomers may or may not be present. It may be advantageous to use more than one monomer, in which case the resulting product may be a copolymer. However, depending on the reactants and reaction conditions used, polymerization may not occur.

EXAMPLES Next, the advantages of the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

In the following catalyst preparations, all operating procedures were performed under vacuum using a glove box or Schlenk method. Chemicals are commercially available (eg, Strem Ch
emical Co. Aldrich Chemical Co.). Unless otherwise noted, methylaluminoxane (MAO) was used as a 10 wt% toluene solution. Methyllithium (MeLi) is 1
Used as a .4M solution or a solid obtained by evaporation of the solvent. Aniline and aniline _{-d 5 (C 6 D 5 NH} 2) is freshly distilled just prior to use. Trimethylsilylmethyllithium was used as a 1.0 M solution in pentane and as a white crystalline solid that crystallized from the solution at -30 C before use. Benzene -d ₆ (C ₆ D ₆₎ and as tetrahydrofuran -d ₈ (THF-d ₈₎ is pre-dried with sodium before use, over sodium / potassium alloy, and stored under vacuum. Pyridine-d ₅ (pyr-d ₅ ) and dichloromethane-d ₂ (CD ₂ Cl ₂ ) were dried over CaH ₂ and vacuum distilled using pre-activated 4Å molecular sieves before use. Pentane, diethyl ether, tetrahydrofuran (THF) and hexamethyldisiloxane (HMDS) were dried over sodium / benzophenone before use.

Trichlorotris (tetrahydrofuran) vanadium (VCl ₃ (THF) ₃ ) and trichlorotris (tetrahydrofuran) titanium (TiCl ₃ (THF) ₃ ) are obtained from the corresponding metal trichlorides (TiCl ₃ and VCl ₃ , respectively). Manufactured by reaction with anhydrous tetrahydrofuran (Manzer, LE Inorganic Synthesis XXI, 135-14
0, John Wiley & Sons (1982), the disclosure of which is incorporated herein.

Trichlorotris (tetrahydrofuran) chromium (CrCl ₃ (THF) ₃ ) is continuously extracted with anhydrous tetrahydrofuran in solid form mixed with a catalytic amount of zinc dust to convert anhydrous chromium trichloride to its tetrahydrofuranate. (Herwig, W .; Zeiss, HH, Journal of Organic Chemistry, Vol. 23, p. 1404, (1958), the disclosure of which is incorporated herein by reference).

The crystalline oxonic acid ([(3,5- (CF_Three)_TwoC₆H_Three)_FourB]^-[H (OEt_Two)_Two]⁺) In ether
, Na [(3,5- (CF_Three)_TwoC₆H_Three)_FourB] was exposed to HCl and [(3,5- (CF_Three)_TwoC₆H_Three)_FourB]^-[H (OEt _Two )_Two]⁺Was synthesized by isolation of This synthesis is disclosed in the following reference: Brookhart, M .; Grant, B .; Volpe, A.F., Organometallics 11, No. 11, 3
920-3922, (1992).

Analytical Methods NMR spectra were recorded using one or more of Bruker AM-250, WM-250 or 400 spectrometers. Chemical shifts reflected the residual proton response of the indicated deuterated solvent.

Fourier transform infrared spectra were recorded on a Mattson Alpha Centauri spectrometer at a resolution of 4 cm ⁻¹ .

UV-VIS spectra were recorded using a Bruins Omega 20 spectrophotometer and a Beckman DU 640 spectrophotometer.

[0044] Mass spectra were obtained from the University of Delaware Mass Spectrometry Facility.

Elemental analysis was performed using Oneida Research Services, Whiteboro, NY 13492 or Schwarz
Kopf Microanalytical Laboratory, Woodside, NY 11377. Note: Elemental analysis of Examples 1A and 1B did not match calculated values. This is probably due to loss of coordinating solvent caused by vigorous pumping under high vacuum.

The room temperature susceptibility was measured using a Johnson-Matthey Magnetic Susceptibility Balance. It uses a modification of the Gouy method. The molar susceptibility was corrected for the diamagnetic force using Pascal's constant, and the effective magnetic moment (μ _eff ) was calculated from the following equation: μ _eff = 2.828 (Txm) ^1/2 . T is the Kelvin temperature, and xm is the molar susceptibility corrected for the diamagnetic force.

In a production flask of 2-N-phenylamino-4-N′-phenylimino-2-pentene, (Ph) ₂ nacnacH, redistilled aniline was equimolar (eq.) Of 2,4-pentanedione with Mix and mix benzene. The mixture was boiled in an oil bath and the azeotrope distilled off (benzene-water) was replaced by benzene until all the water had separated. Then the excess solvent was distilled off. The crude product was redistilled under vacuum (bp about 75 ° C.) to give a crystalline material, which was recrystallized from hexane to give 2-N-phenylamide as yellow microcrystals.
-2'-Penten-4-one was obtained.

The obtained yellow crystal of 2-N-phenylamido-2′-penten-4-one was then used to produce (Ph) ₂ nacnacH according to the above reaction scheme 1. A molar equivalent of triethyloxonium tetrafluoroborate in dichloromethane was added dropwise to 2-N-phenylamido-2'-penten-4-one in the same solvent. The mixture was left for 30 minutes. Then one molar equivalent of aniline in dichloromethane was added. After 1 hour, the solvent was completely removed under vacuum and the residual oil was dissolved in hot ethyl acetate and 2-N-phenylamino-2′-
The pentene-4-phenylimmonium tetrafluoroborate product crystallized.

The free base of the ligand, (Ph) ₂ nacnacH, was prepared from 2-N-phenylamino-2′-pentene-4-phenylimmonium tetrafluoroborate. Potassium hydride (KH
) (Optionally with MeLi) gave about 98% yield of yellow, neutral, deprotonated (Ph) ₂ nacnacH crystals. In another embodiment, a metal salt such as (Ph) ₂ nacnacLi (or (Ph) ₂ nacnacK) is a 2-N-phenylamino-2′-pentene-4-phenylimmonium tetrafluoroborate cation salt And 2 equivalents of Me
Could be formed from Li (or KH). The deuterated products of these compounds are:
It can be formed by replacing the aniline -d ₅ by unlabeled aniline.

Example 1A 2,4-Pentanedi (N-phenyl) iminatodichlorobis-tetrahydrofuran titan, (Ph) ₂ nacnacTiCl ₂ (THF) _{2 , the} corresponding compound having _a deuterated ligand and ( Ph-d _{5) 2} nacnac manufacturing 1.5 g of (6.0 mmol) of (Ph) ₂ nacnacH, was dissolved in 50 ml of tetrahydrofuran and cooled to -30 ° C.. One equivalent (132 mg) of MeLi was added slowly as a solid with stirring. The (Ph) ₂ nacnacLi obtained was added dropwise over a period of 3 hours to 2.223 g (6.0 mmol) of cooled TiCl ₃ (THF) ₃ (solution in 150 ml of THF). Upon cooling, the solution turned from light blue to brown and then dark brown. 50 m of reaction mixture
Concentrate to 1 l, cool to -30 ° C and crystallize. The dark brown microcrystalline powder was collected by filtration and washed several times with cold THF. After drying under vacuum, 2.92 g (95% yield) of (Ph) ₂ na
cnacTiCl ₂ (THF) ₂ was isolated as a microcrystalline brown compound.

The compounds obtained were analyzed and tested and the results are shown in Tables 1A.1-3. The results of single crystal X-ray diffraction are shown in FIG.

[0052]

[Table 1A.1]

Note) (applied for Tables 1A-6) +: Analytical results for corresponding catalyst prepared using deuterated ligand, (Ph-d ₅ ) ₂ nacnac (H) a: For NMR measurements Solvent used b: Solvent used for IR measurement c: Solvent used for UV-VIS measurement Letters after the numerical value of IR indicate the intensity of the indicated peak: vs = very strong, s = strong, m = Medium strength, w = weak

[0054]

[Table 1A.2]

[0055]

[Table 1A.3]

Example 1B 2,4-pentanedi (N-phenyl) iminatodichlorobis-tetrahydrofuran vanadium, (Ph) ₂ nacnacVCl ₂ (THF) ₂ and deuterated ligand (P
Preparation of the corresponding compound with hd- ₅ ) ₂ nacnac: 3.72 mmol (0.93 g) of (Ph) ₂ nacnac (H) were dissolved in 50 mL of THF and cooled to -30 C in a round bottom flask. 3.72 mmol of MeLi solution was added slowly and stirred for 2 hours to obtain a yellow THF solution of (Ph) ₂ nacnacLi with gas evolution. The reaction mixture was stirred until no more bubbling was observed.
And cooled. In a separate round bottom flask, 3.72 mmol (1.37 g) of VCl ₃ (THF) ₃ was dissolved in 150 mL of THF. Then, T of (Ph) ₂ nacnacLi
The HF solution was transferred to a dropping funnel, and a THF solution of VCl ₃ (THF) _{3 was} added dropwise over 3 hours. The solution slowly changed color from dark red to purple-brown and finally dark green. After stirring overnight, the solvent was evaporated to dryness. The resulting brown solid was triturated in ether and extracted with toluene. The brown solution was then filtered and the toluene was removed in vacuo. When the solid was dissolved in THF, it turned dark green. THF
The solution was cooled to -30 C and crystallized. The dark green fine crystalline powder was isolated by filtration and washed several times with cold THF. After drying under vacuum, 1.05 g (55% yield) of (Ph) ₂ nacnacVCl ₂ (THF) ₂ was isolated. The compound obtained was analyzed and tested. The results are shown in Table 1B. 1 to 3. FIG. 2 shows the result of single crystal X-ray diffraction.

[0057]

[Table 1B. 1)

[0058]

[Table 1B. 2]

[0059]

[Table 1B. 3-1]

[0060]

[Table 1B. 3-2]

Example 1C 2,4-pentanedi (N-phenyl) iminatodichlorobis-tetrahydrofuran chromium, (Ph) ₂ nacnacCrCl ₂ (THF) ₂ and deuterated ligand (Ph)
-D ₅₎ preparation of the corresponding compounds according to _{2 nacnac:} (Ph) _{2 nacnacH2.40mmol} a (0.6 g) was dissolved in 50 mL of THF, -3
Cooled to 0 ° C. 2.40 mmol (53 mg) of MeLi were added slowly as a solid. The THF solution of (Ph) ₂ nacnacLi formed in situ was slowly added to a slurry of 2.40 mmol (900 mg) of CrCl ₃ (THF) _{3 in} 150 mL of THF over 3 hours. The color of the solution changed from purple to reddish brown. After stirring at room temperature overnight, the reaction mixture was concentrated to 50 mL, cooled to -30 C and crystallized.
A brown fine crystalline powder was isolated by filtration. After washing several times with cold THF, it was dried under vacuum. (Ph) ₂ nacnacCrCl ₂ (THF) ₂ compound 2.09 mmol (1.08 g)
, 87% yield). The compound obtained was analyzed and tested. The results are shown in Table 1C. 1 to 3. FIG. 3 shows the result of single crystal X-ray diffraction.

[0062]

[Table 1C. 1)

[0063]

[Table 1C. 2]

[0064]

[Table 1C. 3-1]

[0065]

[Table 1C. 3-2]

Example 2A 2,4-pentanedi (N-phenyl) iminatochloromethyl vanadium, (P
h) Preparation of ₂ nacnacV (Cl) (Me): 0.97 mmol (0.500 g) of (Ph) ₂ nacnacVCl ₂ (THF) _{2 of} Example 1B
) Was dissolved in 150 mL of THF, and the solution was cooled to -30 ° C. MeLi (0.9
(7 mmol) in ether solution slowly (Ph) ₂ nacnacVCl ₂ (THF) ₂ in THF
Added to the suspension. This changed the color from dark green to dark reddish brown. After stirring for 5 hours, the reaction mixture was evaporated to dryness. Residual THF was removed by trituration in ether. The brown solid was then extracted with ether, filtered,
LiCl was removed. The ether solution was concentrated, cooled to -30 C and crystallized. The brown fine crystalline powder was filtered and washed with cold pentane. After drying under vacuum, (P
h) 0.202 g (59% yield) of ₂ nacnacV (Cl) (Me) was isolated. The compound obtained was analyzed and tested. The results are shown in Table 2A.

[0067]

[Table 2A]

[0068]Example 2B 2,4-pentanedi (N-phenyl) iminatochlorotrimethylsilylmethyl
Vanadium, (Ph)_TwonacnacV (Cl) (CH_TwoSi (CH_Three)_ThreePreparation of): (Ph) of Example 1B_TwonacnacVCl_Two(THF)_Two0.58mmol (300mg)
Was dissolved in 50 mL of diethyl ether, and the solution was cooled to -30 ° C. Li (CH _Two Si (CH_Three)_Three) (0.58 mmol) in diethyl ether slowly (Ph) _Two nacnacVCl_Two(THF)_TwoWas added to a diethyl ether solution. This clouded the brown solution without observing a color change. After stirring at room temperature overnight, the reaction mixture is
Evaporated to dryness. Dissolve dark brown oil in pentane, evaporate and dry
Was performed twice to remove residual THF. The solid is then extracted with pentane and filtered.
To remove LiCl. Evaporate the solvent again and remove the dark reddish brown oil with a few drops of pentane.
The solution was dissolved in a minimum amount of HMDS together with the solution, cooled to -30 ° C and crystallized. Twice
After the crystallization extraction cycle of (Ph)_TwonacnacV (Cl) (CH_TwoSi (CH_Three)_Three ) Of dark brown crystals (124 mg, 50% yield) were isolated. Analyze the obtained compound
Tested. The results are shown in Table 2B.

[0069]

[Table 2B]

Example 3A Preparation of 2,4-pentanedi (N-phenyl) iminatodimethylvanadium, (Ph) ₂ nacnacVMe ₂ : 5.0 mmol of (Ph) ₂ nacnacVCl ₂ (THF) _{2 of} Example 1B (2. 58 g) were suspended in 150 mL of THF and cooled to -30 ° C. 11.0 mmol of MeLi (2.
2 eq.) Were added slowly. This changed the color from dark green to dark brown. After stirring for 5 hours, the reaction mixture was evaporated to dryness. The operation of dissolving the brown solid in diethyl ether, evaporating and drying was performed twice to remove residual THF. The solid was then extracted with diethyl ether and filtered to remove residual LiC
l was removed. The solution was concentrated to 30 mL of ether, cooled to -30 C and crystallized. After vacuum drying, 1.397 g of brown hexagonal (Ph) ₂ nacnacVMe ₂ containing chloride impurities of (Ph) ₂ nacnacV (Cl) (Me) was isolated. The content of chloride impurities was 18-50%. The compound obtained was analyzed and tested. The results are shown in Table 3A. 1 to 3. FIG. 4 shows the result of single crystal X-ray diffraction.

[0071]

Table 3A. 1)

[0072]

Table 3A. 2]

[0073]

Table 3A. 3-1]

[0074]

Table 3A. 3-2]

Example 3B Preparation of 2,4-pentanedi (N-phenyl) iminatobis-trimethylsilylmethylvanadium, (Ph) ₂ nacnacV (CH ₂ Si (CH ₃ ) ₃ ) ₂ : 1.94 mmol (1.00 g) (Ph) ₂ nacnacVCl ₂ (THF) ₂ [see Example 1B] was dissolved in 150 ml of THF, and the solution was cooled to −30 ° C. To this THF solution was slowly added 3.88 mol (0.366 g) of LiCH ₂ Si (CH ₃ ) ₃ crystals to change the color of the solution from dark green to dark reddish brown. After stirring at room temperature for 4 hours, the reaction mixture was evaporated to dryness. Trituration in pentane to remove residual THF. The dark brown solid was extracted with pentane and filtered to remove LiCl. After removing the solvent from the filtrate, the resulting brown oil was dissolved in HMDS and cooled to -30 ° C. No solid was isolated. However, evaporation of the solvent gave a dark brown oil, namely (Ph) ₂ nacnacV (C
_{H 2 Si (CH 3) 3} ) 2 0.11g (65% yield) was isolated. Analysis of the oil gave the results shown in Table 3B.

[0076]

[Table 3B]

Example 4 Preparation of 2,4-pentanedi (N-phenyl) iminato (OTf) ₂ bis-tetrahydrofuran vanadium, (Ph) ₂ nacnacV (OTf) ₂ (THF) ₂ : 0.52 mmol (270 mg) of ( Ph) ₂ nacnacVCl ₂ (THF) ₂ [see Example 1B]
Dissolved in 0 ml THF. 1.04 mmol (280 mg) of AgOTf was added as a solid to the THF solution. After stirring overnight, the solution was filtered to remove the AgCl _2. The dark green solution was concentrated and crystallized upon cooling to -30 ° C. Dark green (Ph) ₂ nacnacV (OTf
) ₂ (THF) ₂ crystals 340 mg (87% yield) was isolated. The crystals were analyzed and the results shown in Table 4 were obtained.

[0078]

[Table 4]

Example 5A 2,4-Pentanedi (N-phenyl) iminatomethyldiethylethertetrahydrovanadiumtetrakis- (3,5-bis-trifluoromethyl-phenyl) borate, [(Ph) ₂ nacnacVMe Preparation of (Et ₂ O) (THF)] [B (C ₆ H ₃ (CF ₃ ) ₂ ) ₄ ]: 20 ml of 0.30 mmol (100 mg) of (Ph) ₂ nacnacVMe ₂ [see Example 3A]
In diethyl ether and cooled to -30 ° C. In a separate flask,
.30 mmol (310 mg) of H (Et ₂ O) ₂ [B (C ₆ H ₃ (CF ₃ ) ₂ ) ₄ ] was dissolved in 10 ml of diethyl ether and cooled to −30 ° C. (Ph) ₂ nacnacVMe ₂ H (Et ₂ O) ₂ (B (
A solution of C ₆ H ₃ (CF ₃ ) ₂ ) ₄ ] in diethyl ether was slowly added using a pipette. A gas evolved and the color of the solution turned slightly darker brown. From a concentrated diethyl ether solution cooled to -30 ° C containing a few drops of THF, an orange [(Ph) ₂ na
0.21 mmol of cnacVMe (Et ₂ O) (THF)] [B (C ₆ H ₃ (CF ₃ ) ₂ ) ₄ ] crystal (278 mg, yield 69)
%) Was isolated. The obtained compound was subjected to an analytical test, and the results shown in Tables 5A.1 to 3 were obtained. FIG. 5 shows the result of X-ray diffraction of the single crystal.

[0080]

[Table 5A.1]

[0081]

[Table 5A.2]

[0082]

[Table 5A.3-1]

[0083]

[Table 5A.3-2]

Example 5B 2,4-pentanedi (N-phenyl) iminatomethylbis-diethylether vanadium tetrakis- (3,5-bis-trifluoromethyl-phenyl) borate, [(Ph) ₂ nacnacVMe (Et ₂ Preparation of O) ₂ ] [B (C ₆ H ₃ (CF ₃ ) ₂ ) ₄ ]: Prior to the reaction, the dry box was washed with water for 30 minutes to completely remove THF from the inert atmosphere. The same reaction sequence and the same amount of reactants as in Example 5A were used to synthesize (Ph) ₂ nacnacVMe (Et ₂ O) ₂ [B (C ₆ H ₃ (CF ₃ ) ₂ ) ₄ ]. Medium yield (195 mg, 46% yield) from a concentrated diethyl ether solution cooled to -30 ° C.
), And the product was [[Ph) ₂ nacnacVMe (Et ₂ O) ₂ ] [B (C ₆ H ₃ (CF ₃ ) ₂ ) ₄ ] based on the analytical data shown in Table 5B. Is believed to be contained.

[0085]

[Table 5B]

Example 6 Preparation of bis- (2,4-pentanedi (N-phenyl) iminato) chromium (II), ((Ph) ₂ nacnac) ₂ Cr: Preparation 1: 2-N-phenylamino-4- Reaction of N'-phenylimino-3-pentenyldichlorobis-tetrahydrofuranchromium, (Ph) ₂ nacnacCrCl ₂ (THF) ₂ with MeLi: 1.16 mmol (600 mg) of (Ph) ₂ nacnacCrCl ₂ (THF) ₂ [ Example 1C] was dissolved in THF and cooled to -30 ° C. Two molar equivalents of a MeLi solution were added to (Ph) ₂ nacnac
It was added dropwise to the rCl ₂ (THF) ₂ solution. Upon addition of the MeLi solution, the suspension quickly turned brown. After stirring the reaction mixture at room temperature for 4 hours, the solution was evaporated to dryness.
Trituration in ether removed the THF. The resulting solid was extracted with ether and filtered to remove LiCl. The black-green filtrate was then concentrated and cooled to -30 ° C for crystallization. 210 mg (35% yield) of black-green crystals of ((Ph) ₂ nacnac) ₂ Cr were isolated. The obtained compound was analyzed, and the results are shown in Tables 6A.1 to 3. FIG. 6 shows the result of X-ray diffraction of the single crystal.

Preparation 2: Reaction of 2-N-phenylamino-4-N′-phenylimino-2-pentene, (Ph) ₂ nacnacH, with MeLi and CrCl ₂ : 16 mmol (4.0 g) of (Ph) ₂ Nacnac (H) was dissolved in THF and cooled to -30 ° C. 16 mmol (352 mg) of MeLi was added to a solution of (Ph) ₂ nacnacH in THF. To a solution of 8 mmol (983 mg) of CrCl ₂ in THF was added a THF- (Ph) ₂ nacnacLi solution dropwise over 1 hour using a dropping funnel. The reaction mixture was then stirred at room temperature overnight. The solvent was removed by drying and extracted with diethyl ether. The extract was then filtered to remove LiCl. 7 from concentrated diethyl ether solution cooled to -30 ° C
0.09 mmol (3.7 g, 84% yield) of black crystals of ((Ph) ₂ nacnac) ₂ Cr were isolated.

[0088]

[Table 6.1]

[0089]

[Table 6.2]

[0090]

[Table 6.3-1]

[0091]

[Table 6.3-2]Solution and refinement System used SHELXTL (5.03) Solution Direct method Refinement method Full matrix least squares least amount S [w (F₀ ^Two -F_c ^Two)^Two] / S [(wF₀ ^Two)^Two] ^1/2 Hydrogen atom Idealization contribution Weighting scheme w^-1= s^Two(F) +0.0010 Final R index (observed data) R = 8.87%, wR = 21.76% R index (all data) R = 11.77%, wR = 24.49% Goodness of fit 1.100 Data to parameter ratio 17.7: 1 Maximum difference peak 0.892 Maximum difference hall -0.812

Polymerization Experiment Determination of M _w , M _n , M _z and M _p M _w (weight average molecular weight) of polymer sample, M _n (number average molecular weight measured with respect to low end of polymer) , M _z (average molecular weight measured against the high end of the polymer) and M _p (molecular weight at peak position) were determined using a size exclusion chromatography (SEC) column. SEC columns separate polymer solutions into fractions based on three-dimensional molecular size (hydrodynamic volume (Hv)). These fractions have a refractive index (RI) that responds linearly to the concentration of the homogeneous polymer.
Detected by the detector. The molecular weight distribution (MWD) was determined as the primary equivalent molecular weight relative to a primary detection polyethylene (PE) standard [Chevron 9640]. For high density PE (HDPE), the determined molecular weight can be regarded as absolute. For low density PE (LDPE), the average molecular weight (M _w ) is underestimated as being proportional to the additional amount of branching along the backbone. For samples with a fairly constant amount of branching, the molecular weight distributions can be compared to each other on a relative scale. The polymer sample was ground to 20 mesh. 4ml of 8mg +/- 0.2mg sample
Were placed in a small glass container and three separate samples were prepared for one measurement. 4 mL of TCB (containing 500 ppm of an antioxidant to prevent molecular degradation) was added into each small glass container using an automatic solvent dispenser. The sample was placed in a 180 ° C. oven for 4 hours to dissolve. The small glass container was shaken three times within these four hours. This sample was subjected to a test using a Waters 150C chromatography system equipped with three columns of mixed A + 150A Polymer Laboratories (UK). The test measurement was performed under the following conditions. Concentration: 2 mg / mL Injection volume: 400 μL Flow rate: 1 mL / min Column and injector chamber temperature: 150 ° C Test time: 1 hour Calculation method: The weight fraction of the polymer is determined by the flow rate correction based on the flow rate marker peak. I asked for it. Trisec software for 3.00 (Visco
_Mn , _Mw , _Mz , _Mp and D (average values for three separate preparations) were determined by a standard calibration method (Tec).

Determination of Short Chain Branching (SCB) Samples were analyzed using a Varian Unity NMR spectrometer (7 Tesla) equipped with a 10 mm broadband probe tuned to C-13. did. About 0.5 g of the sample was placed in a 10 mm NMR tube, and the tube was filled with a 3: 1 mixture of 1,2,4-trichlorobenzene / deuterated benzene. The sample was warmed to 130 ° C and lysed until a clear solution was formed. After the bubbles and voids in the viscous solution were removed, the sample was submitted for analysis. The sample was placed in the lumen of an NMR magnet and heated to 130 ° C. After reaching thermal equilibrium, the sample was allowed to stabilize for 5 minutes. After locking the sample with deuterium to the deuterated benzene signal to stabilize the magnetic field, increase the resolution and signal-to-noise ratio by shielding the sample's magnetic field and reducing magnetic field inhomogeneities. Was. The sample was pulsed every 5.9 seconds (the relaxation time and the recycle delay were 0.9 seconds and 5 seconds, respectively), giving a total of 2500 transients (4 hours total experiment time). The recorded free induction decay was Fourier transformed to obtain an NMR spectrum. The spectra were tuned and the baseline corrected. The content of short chain branches was determined using specific resonances characteristic of each type of short chain branch (methyl-hexyl or higher branches). Each characteristic resonance and polymer skeleton resonance (27.8-31.5pp
m) and the ratio was expressed as short chain branching per 1000 carbon atoms. The low molecular weight carbon content was determined by the ratio of the integral of the characteristic resonance at 114 ppm to the integral of the polymer backbone.

Determination of Melting Point (Peak DSC MP) Samples were analyzed using a DSC7 differential scanning calorimeter (Perkin-Elmer) equipped with an intercooler. The sample (about 10 mg) was placed in an aluminum dish-shaped container, and an aluminum lid was crimped. The sample was heated twice. Heat history is removed by the first heating, and DS of the sample is heated by the second heating.
C measurements were recorded. The sample is heated from 0 ° C initially at a rate of 20 ° C / min.
C., kept at 170.degree. C. for 5 minutes, and then cooled to 0.degree. C. at a cooling rate of 10.degree. C./min. After holding the sample at 0 ° C. for 1 minute, it was heated again to 170 ° C. at a rate of 20 ° C./min. The second heating scan was recorded. The melting point was determined using the peak. Melting points were generally between 90 and 140 ° C. The area under the curve is considered the heat of fusion of the polyethylene copolymer. The following polymerization reactions that lead to the formation of oligomers are based on FID detectors and Chrompack columns [WCOT ulti-metal 10m x 0.53mm; HT SIMDI
ST CBDF-coated (coating thickness: 0.15 μm)] using an HP 5890 gas chromatograph. The analysis conditions are as follows: helium carrier; 120 ° C. × 1 minute × 10 ° C./min×150° C. × 0 minute; Ramp A: 6.0 ° C./min×350° C. × 0 minute

Example 7 Ethylene polymerization in the presence of (Ph) ₂ nacnacVMe ₂ [B (C ₆ F ₅ ) ₃ ] synthesized in situ in a NMR tube Preparation 1 (in CD ₂ Cl ₂ ) (Ph) ₂ nacnacVMe ₂ 0.0453 mmol (15 mg) (Reference Example 3A) and B (C ₆ F ₅ ) ₃ , 0.045
3 mmol (23 mg) was placed in an NMR tube reactor, and CD ₂ Cl ₂ was introduced in vacuo. Ethylene (1 atm
) Was introduced into an NMR tube, and the tube was closed with a Teflon splicer. After 5 minutes, a ¹ H-NMR spectrum was recorded. Compared to the original spectrum described in Example 3A above, ethylene resonance (δ 5.40 ppm) and a new peak (δ 1.7 ppm) were observed. After 10 minutes, white polyethylene particles precipitated from solution. Ethylene (1 atm) was further introduced into the NMR tube, and the reaction was carried out for 3 hours. ^{Further 1} H-NMR measurement revealed that the spectrum showed all resonance peaks attributable to the catalyst, but the peak of the ethylene monomer almost disappeared. Preparation 2 (C ₆ D in _{6) (Ph) 2 nacnacVMe 2} ( Reference Example ^{3A) 4.53 × 10 - 5 mol} (15mg) and _{B (C 6 F 5) 3} 4.
53 × 10 ^{- 5} mol of (23 mg) placed into an NMR tube and Tsu further Do to put the polymerization reaction of ethylene. With the condensation of C ₆ D _6, dark brown OIL was produced by the reaction (Ph) ₂ nacnacVMe ₂ and _{B (C 6 F 5) 3} . The oil was insoluble in C ₆ D _6. After standing at room temperature for one day, the ethylene monomer peak decreased to about 40% (integrated with the C ₆ B ₆ peak). ¹ H-NMR
The (C ₆ D ₆ ) spectrum showed a broad peak at 2.4 to 0.6 ppm.

Example 8 Polymerization of ethylene in CH ₂ Cl ₂ in the presence of (Ph) ₂ nacnacVMe ₂ and cocatalyst in a Parr reactor (Ph) ₂ nacnacVMe ₂ (Reference Example 3A) ) 0.151 mmol (50 mg) and B (C ₆ F ₅ ) ₃ 0.151 mm
ol (77 mg) was dissolved in 100 ml of CH ₂ Cl ₂ and the solution was transferred into a Parr reactor. Ethylene (700 psig) was introduced into the reactor. After about 5 minutes, the temperature of the reactor reached 120 ° C., so the supply of ethylene was stopped. The pressure gradually decreased under stirring. After stirring for several hours, the reactor was opened to atmospheric pressure. A dark polymer was obtained in the form of a block. The polymer was washed with a methanol / HCl mixture and deionized (DI) water and then dried in a vacuum oven at 60 ° C. overnight. 5.2 g of polymer were obtained. According to the analysis of the polymer, M _w = 547700, M _w / M _n = 2.06 and peak DSC MP =
134.2 ° C.

Example 9 Polymerization of propylene in CD ₂ Cl ₂ in the presence of (Ph) ₂ nacnacVMe ₂ and cocatalyst in a reactor for NMR (Ph) ₂ nacnacVMe ₂ (Reference Example 3A) 4.53 × 10 ^-5 mol and _{B (C 6 F 5) 3} 4.53 × 10 - 5 mol of (23 mg) was dissolved in CD ₂ Cl _2, and transferred to an NMR tube reactor. Propylene (1a
tm) was introduced into the tube reactor. The ¹ H-NMR spectrum after 10 minutes showed no signs of reaction. The reaction was carried out at room temperature for several hours and then at 60 ° C. overnight, without any signs of reaction.

Example 10 1 in CD ₂ Cl ₂ in the presence of (Ph) ₂ nacnacVMe ₂ and cocatalyst in a reactor for NMR
-Hexene polymerization reaction (Ph) ₂ nacnacVMe ₂ [B (C ₆ F ₅ ) ₃ ] was prepared as described in Reference Example 9. Na /
1-Hexene, which had been pre-dried using a K alloy, was vacuum-introduced into an NMR tube reactor.
After 10 minutes, the ¹ H-NMR spectrum was measured and then the reactor was heated at 60 ° C. overnight. Analysis of the resulting product indicated the formation of oligomers (mostly dimers to hexamers), including branched oligomers.

Example 11 Copolymerization reaction of ethylene and 1-hexene in CH ₂ Cl ₂ in the presence of (Ph) ₂ nacnacVMe ₂ and cocatalyst in a Parr reactor (Ph) ₂ nacnacVMe ₂ ( Reference Example 3A) 0.151 mmol (50 mg) and B (C ₆ F ₅ ) ₃ 0.151 mm
ol The (77 mg) was dissolved in a mixture of CH ₂ Cl ₂ 60 ml and 1-hexene 30 ml. This solution was transferred into a Parr reactor. Ethylene (800 psig) was introduced into the reactor. When the temperature of the reactor reached about 120 ° C, the supply of ethylene was stopped. The pressure gradually decreased under stirring. After several hours of stirring, the reactor was opened and a block of polymer was obtained. The block was washed with a methanol / HCl mixture and DI water and then dried overnight in a 60 ° C. vacuum oven. 5.2 g of polymer were obtained. According to polymer analysis, M _w = 1136000, M _w / M _n = 2.42, peak
DSC MP = 131.4 ° C. According to ¹³ C-NMR analysis, no side chain was observed.

Example 12 CD ₂ in the presence of [(Ph) ₂ nacnacVMe (Et ₂ O) (THF)] [B (C ₆ H ₃ (CF ₃ ) ₂ ) ₄ ] in an NMR tube reactor Polymerization reaction of ethylene in Cl ₂ [(Ph) ₂ nacnacVMe (Et ₂ O) (THF)] [B (C ₆ H ₃ (CF ₃ ) ₂ ) ₄ ] (Reference Example 5A) 1.88 × 10 ⁻⁵ m
ol (25 mg) in CD ₂ Cl ₂ was introduced into a NMR tube reactor. ethylene(
1 atm) was introduced into the reactor and closed with a Teflon stopper. After 15 minutes, a fine precipitate of polyethylene was observed. According to the ² H-NMR spectrum, a strong peak of ethylene monomer (δ 5.40 ppm) was observed together with a trace of free diethylene. After overnight reaction at room temperature, several polymer particles were visually observed, and the ¹ H-NMR spectrum showed free diethylene resonance and traces of unreacted ethylene monomer. When this reaction was performed twice more using propylene (1 atm) and 1-hexene instead of ethylene, no polymerization reaction was observed even under heating conditions.

Example 13 CH ₂ Cl in the presence of [(Ph) ₂ nacnacVMe (Et ₂ O) (THF)] [B (C ₆ H ₃ (CF ₃ ) ₂ ) ₄ ] in a Parr reactor the polymerization reaction of ethylene in _{2 [(Ph) 2 nacnacVMe (} Et 2 O) (THF)] [B (C 6 H 3 (CF 3) 2) 4] ( reference example 5A) 0.045 mmol (6
0 mg) in CH ₂ Cl ₂ (100 ml) was introduced into a Parr reactor. Ethylene (700 psig) was introduced into the reactor. After pressurizing the reactor, the ethylene feed was stopped. Under stirring, the pressure of ethylene gradually decreased. After stirring for several hours, the reactor was returned to atmospheric pressure. After stirring for several hours and opening the reactor, a polymer block was observed. The block was washed with a methanol / HCl mixture and DI water and then dried overnight in a 60 ° C. vacuum oven.
2.5 g of polymer were obtained. Analysis of the polymer indicated _Mw = 450600, _Mw / _Mn = 1.96, and peak DSC MP = 135.9.degree.

Example 14 Polymerization of ethylene in CH ₂ Cl ₂ in the presence of (Ph) ₂ nacnacVCl ₂ (THF) ₂ and cocatalyst in a Parr reactor (Ph) ₂ nacnacVCl ₂ (THF) ₂ (Reference Example 1B) 0.776 mmol (40 mg) was dissolved in dry CH ₂ Cl ₂ (100 ml) in a Parr reactor. The color of the solution turned brown. MAO 7.3
g (about 100 molar equivalents) dissolved in toluene (10 wt%) was added.
The color of the solution instantly changed to dark reddish brown. Ethylene (400 psig) was fed into the reactor. The supply of ethylene was stopped when the inside of the reactor was pressurized. The pressure gradually decreased under stirring. After stirring for several hours, the reactor was opened and polymer blocks were seen. The block was washed with a methanol / HCl mixture and DI water and then dried overnight in a 60 ° C. vacuum oven. 4.6 g of polymer were obtained. Analysis of the polymer indicated M _w = 350032 and M _w / M _n = 10.84.

Example 15 Polymerization of ethylene in toluene in the presence of (Ph) ₂ nacnacVCl ₂ (THF) ₂ and cocatalyst in a Parr reactor (Ph) ₂ nacnacVCl ₂ (THF) ₂ 1.20 × 10 ^-5 mol (8 mg) (Reference Example 1B) was dissolved in toluene (50 ml) in a Parr reactor, and then a solution prepared by dissolving 1.2 g (about 100 molar equivalents) of MAO in toluene (10 wt% ) Was added. Ethylene pressure (30
After the polymerization reaction was carried out for 1 hour under the condition that the pressure was kept constant at 0 psig), the supply of ethylene was stopped. The reaction was run for another 1/2 hour to track ethylene uptake. During 1/2 hour the ethylene pressure dropped by 50 psi. The reaction temperature was kept below 60 ° C. using a cooling water circulation system. The resulting product is mixed with a methanol / HCl mixture and
After washing with DI water, it was dried in a vacuum oven at 60 ° C. overnight. 4.7 g of a white polyethylene polymer was obtained. According to the analysis of polyethylene, M _w = 195
8584, M _w / M _n = 1.75 and peak DSC MP = 135.4 ° C.

Comparative Example 1 Polymerization of ethylene in the presence of VCl ₃ (THF) ₃ and a cocatalyst in a Parr reactor VCl ₃ (THF) ₃ 1.20 × 10 ^-4 mol (6 mg) was placed in a Parr reactor It was dissolved in 50 ml of toluene. The color of the solution turned brown and the VCl ₃ (THF) ₃ dissolved somewhat. MAO 1.2g (about 10
Upon addition of a 0 molar equivalent) toluene solution (10 wt%), the color of the solution instantaneously changed to dark reddish brown. The reaction was run under a constant ethylene pressure (300 psig).
After .5 hours, the ethylene feed was stopped and ethylene uptake was followed. 0.5 hours after the ethylene feed was stopped, the pressure dropped 130 psi. In the above reaction process, the reaction temperature was kept lower than 60 ° C. using a water circulation pump. After washing the obtained product with a methanol / HCl mixture and DI water,
In a vacuum oven overnight. 8.0 g of white polyethylene granules were obtained. According to the analysis of the polymer, M _w = 2042158, M _w / M _n = 1.73 and peak DSC MP
= 132.1 ° C.

[0105] The copolymerization reaction of ethylene with 1-hexene in CH ₂ Cl ₂ in the presence of Example 16 Parr reactor at _{(Ph) 2 nacnacVCl 2 (THF} ) 2 with a cocatalyst (Ph) ₂ nacnacVCl ₂ (THF) ₂ (Reference Example 1B) 7.76 × 10 ⁻⁵ mol (40 mg) was added to CH ₂ Cl ₂ (100 m
l), a solution of 7.3 g (about 100 molar equivalents) of MAO in toluene (10 wt%) was added to the solution, and the mixture was transferred into a Parr reactor. 40 ml of dry 1-hexene was added to the reaction mixture. After introducing ethylene (350 psig) into the reactor, the supply of ethylene was stopped. After one minute, the temperature had risen to 52 ° C. The temperature was gradually lowered and kept at 45 ° C., and the reaction was carried out under stirring for 1 hour. When the reactor was opened to atmospheric pressure, the entire inside of the reactor was filled with a white sticky polymer. The obtained product was washed with a methanol / HCl mixture and DI water, and then dried in a vacuum oven at 60 ° C. overnight. 23.6 g of polymer were obtained. Analysis of the polymer indicated M _w = 707048 and M _w / M _n = 212.33. Further, according to ¹³ C-NMR, the total number of carbon atoms in the side chain per 1000 carbon atoms was 48.3.

Example 17 Polymerization of 1-hexene in CH ₂ Cl ₂ in the presence of (Ph) ₂ nacnacV (Me) ₂ and a cocatalyst (Ph) ₂ nacnacV (Me) ₂ (Reference Example 3A) 6.04 × 10 ⁻⁵ mol (20 mg) was dissolved in dry CH ₂ Cl ₂ (40 ml) in an ampoule. After a toluene solution of MAO (about 100 molar equivalents) was added to the (Ph) ₂ nacnacV (Me) ₂ solution in the ampoule, the ampoule was closed with a Teflon stopper. After two freeze / pump / thaw cycles, 5 ml of 1-hexene was introduced into the ampoule. When the reaction mixture was stirred at room temperature for 2 hours, no apparent change was observed in the color and viscosity of the reaction mixture. The temperature of the oil bath containing the ampoule was raised to 80 ° C. and stirring was carried out overnight. Upon cooling to room temperature, the solution turned dark orange and became very viscous. The ampoule was released to atmospheric pressure and the resulting product was washed by adding a MeOH / HCl solution. However, the dark orange color did not disappear. Removal of all volatile constituents by distillation gave a dark brown oil. According to ¹ H-NMR (CDCl ₃ ) analysis of the polymer, peaks were observed at δ2.1, 1.3, 1.2 and 0.8 ppm. Analysis of the resulting product indicated that oligomers, including branched oligomers, were formed (mostly dimers to hexamers).

Example 18 Polymerization of Ethylene in CH ₂ Cl ₂ in the Presence of (Ph) ₂ nacnacTiCl ₂ (THF) ₂ and a Cocatalyst CH in a Schlenk flask (100 ml) equipped with a stir bar ₂ Cl ₂ (50ml)
(Ph) ₂ nacnacTiCl ₂ (THF) ₂ (Reference Example 1A) 3.91 × 10 ⁻⁵ mol (20 mg) was dissolved therein. A toluene solution (10 wt%) of 7.3 g of MAO was added to the brown (Ph) ₂ nacnacTiCl ₂ (THF) ₂ solution, and a Teflon stopper equipped with a needle valve was attached. After two freeze / pump / thaw cycles, ethylene (1 atm) was introduced into the flask at room temperature. The pressure drop every 5 minutes was followed over 1 hour. 160 mg of a white powder of polyethylene was obtained after 1 hour. According to polymer analysis, M _w = 195015, M _w / M _n = 21.11 and peak DSC MP = 130.6 ° C.

[0108]Example 19 (Ph) in Parr reactor_TwonacnacTiCl_Two(THF)_TwoAnd CH in the presence of a cocatalyst_TwoCl_TwoDuring ~
Of ethylene polymerization in water (Ph)_TwonacnacTiCl_Two(THF)_Two(Reference Example 1A) 1.57 × 10^-Fivemol (8mg) to CH_TwoCl_Two(50m
l), and a solution of 1.2 g (about 100 molar equivalents) of MAO in toluene (10 wt%
) Was added and the resulting solution was transferred into a Parr reactor. Ethylene at a constant pressure (30
0 psig), the reaction was carried out for 1 hour, and then ethylene feed was stopped.
The ethylene pressure drop was followed over the next 0.5 hour. However, no decrease in ethylene pressure was observed. The resulting product is mixed with a methanol / HCl mixture and
After washing with DI water, it was dried in a vacuum oven at 60 ° C. overnight. White
6.1 g of polyethylene granules were isolated. According to the analysis of the polymer, M_w= 685963, M _w / M_n= 30.9 and peak DSC M.P. = 13.2 ° C.

[0109] The copolymerization reaction of ethylene with 1-hexene in CH ₂ Cl ₂ in the presence of Example 20 Parr reactor at _{(Ph) 2 nacnacTiCl 2 (THF} ) 2 with a cocatalyst (Ph) ₂ nacnacTiCl ₂ (THF) ₂ (Reference Example 1A) 3.90 × 10 ⁻⁵ mol (20 mg) and MAO 8.
0g was dissolved in a mixture of toluene (about 200 mole equivalents) (10 wt%) 1-hexene (30ml) and CH ₂ Cl ₂ (60ml). This solution was transferred into a Parr reactor. As ethylene (350 psig) was introduced into the reactor, the temperature jumped to 52 ° C within one minute. After 25 minutes, the reaction was stopped because the temperature rose rapidly to 140 ° C. Upon opening the reactor to atmospheric pressure, a light brown rubbery polymer was observed. The obtained product was washed with a methanol / HCl mixture and DI water, and then dried in a vacuum oven at 60 ° C. overnight. 12.5 g of polymer were obtained. According to polymer analysis, M _w = 33882 and M _w / M _n = 218.51, and according to ¹³ C-NMR, the total number of carbon atoms in the side chain per 1000 carbon atoms was 34.6. .

Example 21 Polymerization of 1-hexene in CH ₂ Cl ₂ in the presence of (Ph) ₂ nacnacTiCl ₂ (THF) ₂ and a cocatalyst (Ph) ₂ nacnacTiCl ₂ (THF) ₂ (Reference Example 1A) 3.90 × 10 ^-5 mol (20 mg), MAO (100 equivalents) solution and 1 ml of 1-hexene were added to CH ₂ Cl ₂ (20 ml) in an ampoule, and the ampoule was sealed with a Teflon stopper and reacted. Was done. After stirring at room temperature for 2 hours, the ampoule was stirred at 80 ° C. overnight. Upon cooling to room temperature, the solution turned dark orange and became very viscous. The ampoule was released to atmospheric pressure. The resulting product was washed, but the dark orange color did not disappear. Removal of all volatile constituents by distillation gave a dark brown oil. By analysis of the obtained product,
Formation of oligomers (mostly dimers to hexamers) including branched oligomers was observed.

[0111]Example 22 (Ph) in Parr reactor_TwonacnacTiCl_Two(THF)_TwoAnd toluene in the presence of cocatalyst
Polymerization of ethylene in aqueous solution (Ph)_TwonacnacTiCl_Two(THF)_Two(Reference Example 1A) 1.20 × 10^-Fivemol (8 mg) was dissolved in toluene (50 ml) in a Parr reactor. To this solution was added a toluene solution (10 wt%) of MAO 1.2 g (about 100 molar equivalents). The reaction temperature is controlled by circulating cooling water.
And kept below 60 ° C. After the reaction was carried out for 1 hour under the condition where the pressure was kept constant by ethylene (300 psig), the supply of ethylene was stopped. The reaction was allowed to proceed for another 0.5 hour under stirring to track ethylene uptake. This 0
The pressure dropped 100 psi during .5 hours. The product obtained is mixed with methanol / HCl
After washing with DI water and drying in a vacuum oven at 60 ° C. overnight. Pollier
10.5 g of white granules of styrene were obtained. According to the analysis of the polymer, M_w= 818850, M_w/ M _n = 28.58 and peak DSC M.P. = 134.2 ° C.

Comparative Example 2 Polymerization of TiCl ₃ (THF) ₃ and ethylene in toluene in the presence of a cocatalyst in a Parr reactor TiCl ₃ (THF) ₃ 1.20 × 10 ⁻⁴ mol (6 mg) It was dissolved in toluene (50 ml) in a Parr reactor. A toluene solution (10 wt%) of MAO 1.2 g (about 100 molar equivalents) was added to the TiCl ₃ (THF) ₃ solution. The addition of MAO immediately turned the TiCl ₃ (THF) ₃ solution dark brown.
The reaction temperature was kept below 60 ° C. by circulating cooling water. After the reaction was carried out for one hour under the condition that the pressure was kept constant by ethylene (300 psig), the supply of ethylene was stopped. The reaction was allowed to proceed for a further 0.5 hours, when the pressure dropped slightly by 25 psi. The obtained product was washed with a methanol / HCl mixture and DI water, and then dried in a vacuum oven at 60 ° C. overnight. White granular polymer 3.
4 g were obtained. According to analysis of the polymer, M _w = 1479060, M _w / M _n = 153.12 and peak
DSC MP = 134.2 ° C.

Example 23 Polymerization of ethylene in CH ₂ Cl ₂ in the presence of (Ph) ₂ nacnacCrCl ₂ (THF) ₂ and cocatalyst in a Parr reactor (Ph) ₂ nacnacCrCl ₂ (THF) ₂ (Reference Example 1C) 7.76 × 10 ⁻⁵ mol (40 mg) and MAO 7.
3 g (about 100 molar equivalents) of a toluene solution (10 wt%) was dissolved in CH ₂ Cl ₂ (100 ml),
The resulting solution was transferred into a Parr reactor. Ethylene (400 psig) was introduced into the reactor. When the reactor was pressurized, the ethylene feed was stopped. Under stirring, the temperature gradually increased and the maximum temperature reached 110 ° C. Thereafter, the temperature gradually decreased. After stirring for 30 minutes, a white powder of polyethylene was obtained. The obtained powder was washed with a methanol / HCl mixture and DI water, and then dried in a vacuum oven at 60 ° C. overnight. 6.0 g of a white polymer was obtained. According to the analysis of the polymer, M _w = 48613
And M _w / M _n = 22.84.

Example 24 Polymerization of ethylene in toluene in the presence of (Ph) ₂ nacnacCrCl ₂ (THF) ₂ and cocatalyst in a Parr reactor (Ph) ₂ nacnacCrCl ₂ (THF) ₂ Example 1C) 1.20 × 10 ⁻⁵ mol (8 mg) and MAO 1.2
g (about 100 molar equivalents) of a toluene solution (10 wt%) was dissolved in toluene (50 ml) in a Parr reactor. Ethylene (300 psig) was introduced into the reactor. After the stirring was performed for 1 hour under a condition where the pressure of ethylene was kept constant, the supply of ethylene was stopped. Over the next 45 minutes, the ethylene pressure dropped 100 psi. The resulting product was washed with a methanol / HCl mixture and DI water, followed by 60
Dry overnight in a vacuum oven at ℃. 10.5 g of a white solid polymer was isolated. According to the analysis of the polymer, M _w = 1157039, M _w / M _n = 72.81 and peak DSC MP = 13
It was 4.9 ° C.

Comparative Example 3 Polymerization of CrCl ₃ (THF) ₃ and ethylene in toluene in the presence of a cocatalyst in a Parr reactor CrCl ₃ (THF) ₃ 1.20 × 10 ^-4 mol (6 mg) It was dissolved in toluene (50 ml) in a Parr reactor. A toluene solution (10 wt%) of MAO 1.2 g (about 100 molar equivalents) was added to the CrCl ₃ (THF) ₃ solution. Even after the addition of MAO and stirring for 10 minutes, the color of the solution was light brown, and solid CrCl ₃ (THF) ₃ remained. The reaction was carried out for 1 hour under the condition that the pressure was kept constant by supplying ethylene (300 psig), and then the supply of ethylene was stopped, and no detectable pressure drop was observed over the next 30 minutes.
The reaction temperature was kept substantially constant over the entire reaction time without cooling (about
23 ° C). The obtained product was washed with a methanol / HCl mixture and DI water, and then dried in a vacuum oven at 60 ° C. overnight. 0.5 g of polyethylene was obtained. Analysis of the polymer indicated _Mw = 1319817, _Mw / _Mn = 37.88 and the peak DSC MP = 133.3.degree.

[0116] The copolymerization reaction of ethylene with 1-hexene in CH ₂ Cl ₂ in the presence of Example 25 Parr reactor at _{(Ph) 2 nacnacCrCl 2 (THF} ) 2 with a cocatalyst (Ph) ₂ nacnacCrCl ₂ (THF) ₂ (Reference Example 1C) 7.76 × 10 ⁻⁵ mol (40 mg) and MAO 7.
5 g (about 100 molar equivalents) of a toluene solution (10 wt%) was added to 1-hexene (4
0 ml) and CH ₂ Cl ₂ (60 ml). Ethylene (350 psig) was introduced into the Parr reactor as described in Example 22. 8.7 g of a white powdery polymer was obtained. According to analysis of the polymer, M _w = 9659, M _w / M _n = 7, peak DSC MP = 109.6 ° C.
And SCB = 16.

Example 26 Copolymerization of ethylene and propylene in the presence of (Ph) ₂ nacnacCrCl ₂ (THF) ₂ and co-catalyst in a Parr reactor (Ph) ₂ nacnacCrCl ₂ (THF) ₂ 8 mg and 100 mol An equivalent amount of the MAO solution was dissolved in toluene (50 ml) in a Parr reactor. A gas mixture of ethylene and propylene (100 psig) was introduced into the reactor. After stirring for 3 hours, the reaction was stopped. The obtained product was washed with a methanol / HCl mixture and DI water, and then dried in a vacuum oven at 60 ° C. overnight. 250 mg of a white rubbery polymer was isolated. According to analysis of the polymer, M _w = 147054, M _w / M _n = 82.14, peak DSC MP = 95.1, 113.8 and
125.1 ° C and SCB = 9.69.

Example 27 Polymerization of Propylene in the Presence of (Ph) ₂ nacnacCrCl ₂ (THF) ₂ and a Cocatalyst in a Parr Reactor The polymerization of propylene was carried out using reaction conditions similar to those described above. The properties of the resulting product could not be easily determined by the analytical techniques used here. The properties of the products obtained in experiments with the corresponding vanadium and titanium catalysts could not be easily determined either.

Example 28 Copolymerization of ethylene and propylene in the presence of (Ph) ₂ nacnacVCl ₂ (THF) ₂ and co-catalyst in a Parr reactor (Ph) ₂ nacnacVCl ₂ (THF) ₂ 8 mg and 100 mol An equivalent amount of the MAO solution was dissolved in toluene (50 ml) in a Parr reactor. A gas mixture of ethylene and propylene (100 psi) was introduced into the reactor. After stirring for 3 hours, the reaction was stopped. The product was washed and dried to isolate 800 mg of a white gummy polymer. According to the analysis of the polymer, _Mw = 1476492, _Mw / _Mn = 3.94, peak DSC MP = 117.4 ° C and SC
B = 14.88.

Although specific embodiments of the present invention have been described in the foregoing examples, those skilled in the art will readily understand or conceive of many of these variations. Therefore, the present invention is limited only by the technical idea and the technical scope described in the claims.

[Brief description of the drawings]

FIG. 1 is a view showing a crystal structure of (Ph) ₂ nacnacTiCl ₂ (THF) ₂ prepared in Example 1A.

FIG. 2 is a view showing a crystal structure of (Ph) ₂ nacnacVCl ₂ (THF) ₂ prepared in Example 1B.

FIG. 3 is a view showing a crystal structure of (Ph) ₂ nacnacCrCl ₂ (THF) ₂ prepared in Example 1C.

FIG. 4 is a view showing a crystal structure of (Ph) ₂ nacnacVMe ₂ prepared in Example 3A.

FIG. 5 (Ph) prepared in Example 5A._TwonacnacVMe_Two(Et_TwoO) (THF) [B (C₆H_Three(CF _Three )_Two)_FourFIG. 3 is a diagram showing a crystal structure of the above-mentioned formula (however, BArF anion is not shown).

FIG. 6 is a view showing a crystal structure of ((Ph) ₂ nacnac) ₂ Cr prepared in Example 6.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 10/00 C08F 10/00 (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM ), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, G D, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG , MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, UZ, VN, YU, ZW (72) Inventor Woo-Kyu Kim United States 08807 Sunny Slope Road, Bridgewater, NJ 706 F term (reference) 4H049 VN01 VN05 VP01 VQ35 VR24 VR32 VR52 VU14 4H050 AB40 WB14 WB17 4J028 AA01A AB00A AB01A ACA AC02A AC09A AC19A AC31A AC32A AC38A AC41A AC42A AC45A BA01B BB00B BB01B BC03B BC04B BC05B BC08B BC11B BC12B BC15B BC16B BC17B BC18B BC25B EB02 EB04 EB05 EB09 EB17 FA01 A04A04A04A04A04A04A04A04A04A04A04P

Claims (52)

[Claims] (1) Formula (II): Wherein R and R ′ are each a hydrogen atom or a substituted or unsubstituted, branched or unbranched hydrocarbyl or organosilyl group, and R ¹ , R ² and R ³ are each a hydrogen atom, Or a substituted or unsubstituted, branched or unbranched hydrocarbyl group. A catalyst system useful for polymerizing olefin monomers, comprising a monoanionic bidentate ligand represented by the following formula: 2. The catalyst system according to claim 1, wherein the monoanionic ligand coordinates to a Group IIIB, IVB, VB, VIB, VIIB or VIII transition metal. 3. The catalyst system according to claim 2, wherein the metal is a group IVB, VB or VIB transition metal. 4. The catalyst system according to claim 3, wherein the transition metal is selected from the group consisting of titanium, vanadium and chromium. 5. The catalyst system according to claim 1, wherein R and R ′ are each a hydrogen atom or a group selected from the group consisting of alkyl, aryl, alkylaryl, arylorganosilyl, and alkylorganosilyl. 6. The catalyst system according to claim 5, wherein the group has a carbon atom directly bonded to nitrogen, which bonds at least two carbon atoms. 7. R and R ′ are each a hydrogen atom or ethyl, isopropyl, phenyl, 2,6-isopropylphenyl, 2,6-dimethylphenyl,
The catalyst system according to claim 1, which is a 2,6-diethylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl or 2-t-butylphenyl group. 8. R ¹ and R ² are each a hydrogen atom or a group having 1 to 1 carbon atoms.
The catalyst system according to claim 1, which is an alkyl group of 6. 9. The catalyst system according to claim 1, wherein R ¹ and R ² are each a hydrogen atom or a methyl group. 10. The catalyst system according to claim 1, further comprising a metal alkyl co-catalyst. 11. The co-catalyst is an alkylaluminum compound.
0. The catalyst system according to 0. 12. The catalyst system according to claim 11, wherein the alkylaluminum compound includes a trialkylaluminum or an aluminoxane. 13. The aluminoxane of claim 11, wherein the aluminoxane is selected from the group consisting of ethyl aluminoxane, isobutyl aluminoxane, and methyl aluminoxane.
3. The catalyst system according to 1. 14. The catalyst system according to claim 11, wherein the alkylaluminum compound is triethylaluminum. 15. Formula (I): Wherein R and R ′ are each a hydrogen atom, or a substituted or unsubstituted, branched or unbranched hydrocarbyl or organosilyl group; R ¹ , R ² and R ³ are each a hydrogen atom, Or a substituted or unsubstituted, branched or unbranched hydrocarbyl group; M is a group IIIB, IVB, VB, VIB, VIIB or Group VIII transition metal; A ligand such as a hydrogen atom, or a substituted or unsubstituted hydrocarbyl, halogeno, aryloxide, arylorganosilyl, alkylorganosilyl, amide, arylamide, phosphide or arylphosphide group, or two T groups. L is jointly an alkylidene or cyclometalated hydrocarbyl bidentate ligand; Be Joka ligand; optionally present X is a relatively weakly coordinating anion; a = 0 to 4, with b = 0 to 4, is a + b ≦ 4. ] The compound useful as a catalyst shown by these. 16. The compound according to claim 15, wherein M is a group IVB, VB or VIB transition metal. 17. The catalyst system according to claim 15, wherein M is selected from the group consisting of titanium, vanadium and chromium. 18. The compound according to claim 15, wherein R and R ′ are each a hydrogen atom or a group selected from the group consisting of alkyl, aryl, alkylaryl, arylorganosilyl, and alkylorganosilyl. 19. The compound of claim 18, wherein said group has a carbon atom directly attached to the nitrogen, linking at least two carbon atoms. 20. R and R ′ are each a hydrogen atom or ethyl, isopropyl, phenyl, 2,6-isopropylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 4-methylphenyl, The compound according to claim 15, which is a 4,6-trimethylphenyl or 2-t-butylphenyl group. 21. The compound according to claim 15, wherein R ¹ , R ² and R ³ are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. 22. The compound according to claim 15, wherein R ¹ , R ² and R ³ are each a hydrogen atom or a methyl group. 23. The compound according to claim 15, wherein R ³ is hydrogen. 24. The compound according to claim 23, wherein R ¹ and R ² are each a methyl group. 25. X is a BArF ⁻ , (phenyl) ₄ B ⁻ , (C ₆ H ₅ ) ₄ B ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , SbF ₆ ⁻ , triflate, or p-tosylate group. Item 15
The compound according to the above. 26. The compound according to claim 15, wherein X is a BArF ⁻ , (C ₆ H ₅ ) ₄ B, PF ₆ ⁻ , BF ₄ ⁻ , or SbF ₆ ⁻ group. 27. The compound according to claim 15, wherein at least one L is a ligand containing an oxygen, nitrogen, phosphorus or sulfur atom having a non-bonded pair of electrons. 28. The compound of claim 27, wherein said ligand comprises an ether, amine, phosphine or thioester. 29. The ligand according to claim 2, wherein the ligand comprises THF or pyridine.
9. The compound according to 8. 30. The method of claim 15, wherein at least one T is a methyl, ethyl, propyl, butyl, amyl, isoamyl, hexyl, isobutyl, heptyl, octyl, nonyl, decyl, cetyl, 2-ethylhexyl, or phenyl group. The compound according to the above. 31. The compound of claim 15, wherein at least one T is a chloro, bromo, fluoro, and iodo group. 32. The compound according to claim 15, wherein at least one T is a chloro group. 33. The compound according to claim 15, wherein at least one T is an alkoxide or aryloxide group. 34. The compound of claim 15, wherein at least one T is each methoxide or ethoxide. 35. The compound according to claim 15, wherein a = 2. 36. The compound according to claim 35, wherein b = 2. 37. A method of polymerizing at least one olefin monomer and / or oligomer, wherein the temperature and the temperature are such as to induce polymerization of the at least one monomer and / or oligomer to produce a polymer product. Contacting the catalyst system with at least one monomer and / or oligomer under pressure conditions, wherein the catalyst system comprises a compound of formula (I): Wherein R and R ′ are each a hydrogen atom, or a substituted or unsubstituted, branched or unbranched hydrocarbyl or organosilyl group; R ¹ , R ² and R ³ are each a hydrogen atom, Or a substituted or unsubstituted, branched or unbranched hydrocarbyl group; M is a group IIIB, IVB, VB, VIB, VIIB or Group VIII transition metal; A ligand such as a hydrogen atom, or a substituted or unsubstituted hydrocarbyl, halogeno, aryloxide, arylorganosilyl, alkylorganosilyl, amide, arylamide, phosphide or arylphosphide group, or two T groups. L is jointly an alkylidene or cyclometallated hydrocarbyl bidentate ligand; Be Joka ligand; optionally present X is a relatively weakly coordinating anion; a = 0 to 4, with b = 0 to 4, is a + b ≦ 4. ] The method containing the catalyst compound shown by these. 38. The method of claim 37, further comprising using the catalyst compound with a metal alkyl co-catalyst. 39. The co-catalyst is an alkylaluminum compound.
9. The method according to 8. 40. The method according to claim 39, wherein the alkylaluminum compound comprises a trialkylaluminum or an aluminoxane. 41. The aluminoxane is selected from the group consisting of ethyl aluminoxane, isobutyl aluminoxane, and methyl aluminoxane.
The method described in. 42. The method according to claim 40, wherein the alkylaluminum compound is triethylaluminum. 43. The method of claim 37, wherein said contacting is performed at a temperature from about -100 ° C to about 200 ° C. 44. The method of claim 37, wherein said contacting is performed at a temperature of about 30-135 ° C. 45. The method of claim 37, wherein said contacting is performed at a pressure between about atmospheric pressure and about 1000 psig. 46. The method of claim 37, wherein said contacting is under a pressure of about 20-800 psig. 47. A process for producing a catalyst, comprising the steps of formula (III): A compound represented by the formula (I) is brought into contact with a transition metal-containing compound to give a compound of the formula (I): Wherein R and R ′ are each a hydrogen atom, or a substituted or unsubstituted, branched or unbranched hydrocarbyl or organosilyl group; R ¹ , R ² and R ³ are each a hydrogen atom, Or a substituted or unsubstituted, branched or unbranched hydrocarbyl group; M is a Group IIIB, IVB, VB, VIB, VIIB or VIII transition metal; and T is each a monovalent anionic group. A ligand such as a hydrogen atom, or a substituted or unsubstituted hydrocarbyl, halogeno, aryloxide, arylorganosilyl, alkylorganosilyl, amide, arylamide, phosphide or arylphosphide group, or two T groups. L is jointly an alkylidene or cyclometallated hydrocarbyl bidentate ligand; Be Joka ligand; optionally present X is a relatively weakly coordinating anion; a = 0 to 4, with b = 0 to 4, is a + b ≦ 4. ] Producing the catalyst compound shown by these. 48. The method according to claim 47, wherein the transition metal-containing compound contains at least one metal corresponding to the transition metal represented by M. 49. The method according to claim 48, wherein the metal is a Group IVB, VB or VIB transition metal. 50. The catalyst system according to claim 49, wherein the transition metal is selected from the group consisting of titanium, vanadium and chromium. 51. The method of claim 47, wherein the transition metal is a transition metal salt selected from the group consisting of a transition metal halide, a transition metal carboxylate, a transition metal alkoxide, and a transition metal sulfonate. 52. The method of claim 47, wherein the transition metal is a transition metal halide selected from the group consisting of a metal salt of dichloride, a metal salt of trichloride, and a metal salt of tetrachloride.