KR20190003835A - Quinolinyldiamido transition metal complexes, preparation and uses thereof - Google Patents

Abstract

 The present invention discloses quinolinyldiamido transition metal complexes for use in alkene polymerization to produce multimodal polyolefins.

Description

Quinolinyldiamido transition metal complexes, preparation and uses thereof

Inventor (s) : Hagar Dorn John Al., Pala Foxy Patrick J., Jiang Pei Jun, Gao Yao Hua, Chen Xin, Goryunov Georgi P., Sarikov Mikhail I, Uvorskiy Dmitry V., Kop Alexander Jet.

Priority claim

This application claims the benefit of and priority to USSN 62 / 357,033, filed June 30, 2016, and EP 16185512.7, filed August 24, 2016, all of which are hereby incorporated by reference.

Field of invention

The present invention relates to quinolinyldiamido transition metal complexes and intermediates and processes for their use in the preparation of such quinolinyldiamido complexes. Transition metal complexes can be used as catalysts for alkene polymerization processes.

Pyridylamines have been used to prepare tetra complexes which are useful transition metal components in the polymerization of alkenes, for example, in US 2002/0142912; US 6,900,321; And US 6,103,657; Where ligands have been used in complexes where the ligand is coordinated to a transition metal atom in a two-headed manner.

WO 2005/095469 describes a catalyst compound that uses a tridentate ligand through two nitrogen atoms (one amido and one pyridyl) and one oxygen atom.

US 2004/0220050 A1 and WO 2007/067965 disclose complexes in which ligands are coordinated in a three-way fashion via two nitrogens (one amido and one pyridyl) and one carbon (aryl anion) donor.

An important step in the activation of these complexes is the introduction of alkenes into the metal-aryl linkages of the catalyst precursor (Froese, RDJ et al., J. Am. Chem. Soc., 2007, 129, pp. 7831-7840) 7 < / RTI > source chelate ring.

WO 2010/037059 discloses pyridine containing amines for use in pharmaceutical applications.

US 8,158,733 discloses 2- (2-aryloxy) -8-anilinoquinoline, 2,8-bis (2-aryloxy) quinoline, and 2,8- bis ≪ / RTI > aryloxy) dihydroquinoline ligands.

US 2012/0016092 discloses a catalyst composition comprising a 2-amino-8-anilinoquinoline and a 2-aminoalkyl-8-anilinoquinoline ligand having a one-atom linker between nitrogen donors at two positions of a quinoline and a quinoline ring .

[Organometallics, 2012, 31, p. 3241 by Hu et al. Describes a catalyst composition containing a 2-aminoalkyl-8-quinolinolato ligand that is not characterized by a 3-terminal NNN donor ligand.

Organometallics, 2013, 32, p. 2685 by Nifant'ev et al. Describes a catalyst composition containing a 2,8-bis (2-aryloxy) dihydroquinoline ligand that is not characterized by a 3-terminal NNN donor ligand.

[Dalton Transactions, 2013, 42, p. 1501 by Nifant'ev et al. Describes a catalyst composition containing a 2-aryl-8-arylaminoquinoline ligand that is not characterized by a 3-terminal NNN donor ligand.

US 7,858,718 describes a catalyst composition containing a 2-aryl-8-anilinoquinoline ligand that is not characterized by a 3-side NNN donor ligand.

US 7,973,116 describes pyridyldiamide ligands, for example, catalyst compositions containing pyridine based ligands that are not quinoline based ligands.

New catalyst compounds are still needed to broaden the range of catalyst complexes available for good performance in alkene polymerization. Performance refers to the amount of polymer produced (generally referred to as " activity ") per unit weight of the catalyst under typical polymerization conditions; Molecular weight and molecular weight distribution achieved at a given temperature; And / or higher alpha-olefins in terms of the degree of stereoregular arrangement.

There is also a need in the art for new catalysts with high activity that can produce highly crystalline tactic (e.g., isotactic) propylene polymers.

Summary of the Invention

The present invention relates to novel transition metal complexes having a 3-side NNN ligand. The present invention also relates to quinolinyl diamide and related transition metal complexes represented by the following formula (I) or (II): < EMI ID =

In the formula,

M is a 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 metal;

J is a triatomic length bridge between quinoline and amido nitrogen;

E is selected from carbon, silicon, or germanium;

X is an anionic leaving group;

L is a neutral Lewis base;

R ¹ and R ¹³ is independently selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, and silyl groups;

R ² to R ¹² are independently selected from the group consisting of hydrogen, hydrocarbyl, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyl, halogen, and phosphino;

n is 1 or 2;

m is 0, 1, or 2;

n + m is 4 or less;

Any two adjacent R groups (e.g., R ¹ and R ^2, R ² and R ^3, etc.) is coupled to which they are attached may form a substituted or unsubstituted hydrocarbyl or heterocyclic ring ring, the ring is 5 , 6, 7, or 8 ring atoms and substitutions on the rings may combine to form additional rings;

Any two X groups may be joined together to form a dianionic group;

Any two L groups may be joined together to form a two-terminal Lewis base;

The X group may be bonded to the L group to form a monoanionic bidentate group.

The present invention also relates to a process for preparing said complexes, a process for preparing intermediates of said complexes and a process for polymerizing olefins using said complexes.

Figure 1 shows the line drawing of the eight quinolinyldiamide complexes prepared in the experimental part.
Figure 2 shows an example of a quinolinyldiamine ligand prepared in the experimental part.
Figure 3 shows a diagram of a quinolinyldiamide ligand and a metal complex containing a condensed dihydronaphthalene linker group.
Figure 4 shows a (Q5) of the solid state structure HfMe ₂ as determined by single crystal X-ray diffraction.

details

This document describes transition metal complexes. The term complex is used to describe molecules in which ancillary ligands are coordinated to a central transition metal atom. The ligand is bound to the transition metal in a bulky and stable manner so as to maintain its influence during use of the catalyst, such as polymerization. The ligand can be coordinated to the transition metal by covalent bonding and / or electron donating coordination or intermediate bonding. Transition metal complexes are generally activated from the transition metal using activators which are believed to produce cations as a result of the removal of anionic groups, often referred to as leaving groups, to perform their polymerization or oligomerization functions.

As used herein, the periodic table numbering scheme is a new notation as set forth in Chemical and Engineering News, 63 (5), 27 (1985).

As used herein, Me is methyl, Et is ethyl, Bu is butyl, t-Bu and t-Bu are tertiary butyl, Pr is propyl, iPr and iPr are isopropyl, Cy is cyclo Hexyl, THF (also referred to as thf) is tetrahydrofuran, Bn is benzyl, and Ph is phenyl. Room temperature is 23 ° C unless otherwise specified.

Unless otherwise indicated, the term " substituted " generally means that the hydrogen of the substituted species is replaced by a different group of atoms or atoms. For example, methyl-cyclopentadiene is a cyclopentadiene substituted with a methyl group. Likewise, picric acid may be described as a phenol substituted with three nitro groups, or alternatively benzene substituted with one hydroxy and three nitro groups.

The terms " hydrocarbyl radical "," hydrocarbyl ", and " hydrocarbyl group " are used interchangeably throughout this document. Likewise, the terms " group, "" radical, " and " substituent " are also used interchangeably herein. For purposes herein, a "hydrocarbyl radical" is defined as a C ₁ -C ₁₀₀ radical which can be linear, branched or cyclic and, when cyclic, aromatic or non-aromatic.

Substituted hydrocarbyl radical is a hydrocarbyl which at least one hydrogen atom at least one functional group of the radical, for example F, Cl, Br, I, C (O) R *, C (O) NR * 2, C (O) OR _{^{*, NR * 2, OR *}} , SeR *, TeR *, PR * 2, AsR * 2, SbR * 2, SR *, BR * 2, SiR * 3, GeR * 3, SnR * 3, PbR * 3, , Where R ^* is independently hydrogen or a hydrocarbyl radical, and two or more R ^* may be joined together to form a substituted, unsubstituted, partially unsaturated or aromatic cyclic or polycyclic ring structure Or a hydrocarbyl radical in which at least one heteroatom is inserted into the hydrocarbyl ring.

The term " catalyst system " is defined as meaning complex / activator pair. When used to describe these pairs before the " catalytic system " is activated, it means an activator and, optionally, a catalytic complex inactivated with a co-activator (precatalyst). When used to describe these pairs after activation, it refers to activated complexes and activators or other charge balance moieties. The transition metal compound may be neutral as in a pre-catalyst, or it may be a charged species with counter ions as in an activated catalyst system.

The term " complex " may also be referred to as a catalyst precursor, a precatalyst, a catalyst, a catalyst compound, a transition metal compound or a transition metal complex. These words are used interchangeably. Activators and cocatalysts are also used interchangeably.

Scavengers are compounds that are typically added to scavenge impurities to promote polymerization. Some scavengers may also act as activators and may be referred to as activators. A non-scavenger co-activator may also be used with the activator to form an active catalyst. In some embodiments, the co-activator may form a pre-mixed alkylated transition metal compound with the transition metal compound.

For purposes herein, an " olefin " which is alternatively referred to as an " alkene " is a linear, branched or cyclic compound comprising carbon and hydrogen having at least one double bond. For purposes of this specification and the appended claims, when a polymer or copolymer is referred to as comprising an olefin, the olefin present in such a polymer or copolymer is a polymerized form of an olefin. For example, if the copolymer is referred to as having a " propylene " content of from 35 wt% to 55 wt%, the mer units in the copolymer are derived from propylene in the polymerization reaction, Is present in an amount of from 35% to 55% by weight, based on the total weight of the composition. The higher? -Olefins are defined as? -Olefins having 4 or more carbon atoms. For purposes of the present invention, ethylene is considered to be an alpha-olefin.

For purposes herein, "polymer" has two or more identical or different "mer" units. A " homopolymer " is a polymer having the same mer units. &Quot; Copolymer " is a polymer having two or more mer units that are different from each other. A " terpolymer " is a polymer having three mer units that are different from each other. " Different " in the context of a mer unit indicates that the mer units are different from one another or isomerically different by at least one atom. Thus, as used herein, the definition of a copolymer includes ternary copolymers and the like. &Quot; propylene polymer " or " propylene copolymer " is a polymer or copolymer comprising at least 50 mol% propylene derived units, or Copolymers and the like.

As used herein, Mn is number average molecular weight, Mw is weight average molecular weight, Mz is z average molecular weight, wt% is weight percent, and mol% is mole percent. The molecular weight distribution (MWD), also referred to as polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise specified, all molecular weight units (e.g., Mw, Mn, Mz) are reported in g / mol.

All melting points (T _m ) are DSC second melts unless otherwise specified.

A "ring carbon atom" is a carbon atom that is part of a cyclic ring structure. By this definition, the benzyl group has 6 ring carbon atoms and para-methyl styrene also has 6 ring carbon atoms.

The term " aryl " or " aryl group " means, but is not limited to, six carbon aromatic rings including phenyl, 2-methyl-phenyl, xylyl, 4-bromo-xylyl and substituted variants thereof do. Likewise, heteroaryl means an aryl group in which one ring carbon atom (or two or three ring carbon atoms) is replaced by a heteroatom, preferably N, O, or S.

The term " ring atom " means an atom that is part of a cyclic ring structure. By this definition, the benzyl group has 6 ring atoms and the tetrahydrofuran has 5 ring atoms.

A heterocyclic ring is a ring having a heteroatom in the ring structure as opposed to a heteroatom-substituted ring in which hydrogen on the ring atom is replaced by a heteroatom. For example, tetrahydrofuran is a heterocyclic ring and 4-N, N-dimethylamino-phenyl is a heteroatom-substituted ring. Substituted heterocyclic ring, for example F, Cl, Br, I, C (O) at least one hydrogen atom hydrocarbyl group, substituted hydrocarbyl group or the group of the heterocyclic ring ^{R *, C (O) NR} * ^{_{2, C (O) OR *}} , NR * 2, OR *, SeR *, TeR *, PR * 2, AsR * 2, SbR * 2, SR *, BR * 2, SiR * 3, GeR * 3, SnR ^* ₃ , PbR ^* ₃ , etc. where R ^* is independently hydrogen or a hydrocarbyl radical and at least two R ^* are bonded together to form a saturated, partially unsaturated or aromatic cyclic or polycyclic Which may form a cyclic structure.

As used herein, the term " aromatic " also refers to pseudo-aromatic heterocycles which have similar properties and structures (nearly planar) to aromatic heterocyclic ligands but which, by definition, are non-aromatic heterocyclic substituents; Likewise, the term aromatic also refers to a substituted aromatic.

Catalyst compound

The present invention relates to a quinolinyldiamido transition metal complex in which a triplet linker is used between the quinoline and the nitrogen donor at the two positions of the quinoline ring. This has been found to be an important aspect because the use of a tri-atom linker is believed to result in a metal complex having a 7-membered chelate ring that is not co-planar with other 5-membered chelate rings. The resulting complex is believed to be effectively chiral (C ₁ symmetric) even if there is no permanent stereocenter. This is a preferred catalyst characteristic for the production of, for example, isotactic polyolefins.

The present invention also relates to quinolinyldiamido transition metal complexes represented by the formula (I), preferably the formula (II), preferably the formula (III)

The complex of claim 1 wherein the complex is further represented by the formula:

In the formula,

M is a 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 Group metal (preferably a Group 4 metal);

J is a group containing a group comprising a triatomic length bridge between quinoline and amido nitrogen, preferably up to 50 non-hydrogen atoms;

E is carbon, silicon, or germanium;

X is an anionic leaving group (e.g., a hydrocarbyl group or a halogen);

L is a neutral Lewis base;

R ¹ and R ¹³ is independently selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, and silyl groups;

^{R 2, R 3, R 4} , R 5, R 6, R 7, R 8, R 9, R 10, R 10 ', R 11, R 11', R 12, and R ¹⁴ are independently hydrogen, hydrocarbyl Carbocycle, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyl, halogen, or phosphino;

n is 1 or 2;

m is 0, 1, or 2;

n + m is 4 or less;

Any two R groups (e.g., R ¹ and R ² , R ² and R ³ , R ¹⁰ , R ^11, etc.) may be combined to form a substituted hydrocarbyl, an unsubstituted hydrocarbyl, a substituted heterocyclic, or an unsubstituted heterocyclic, saturated or unsaturated ring, 6, 7, or 8 ring atoms and substitutions on the rings may combine to form additional rings;

Any two X groups may be joined together to form a back ionic group;

Any two L groups may be joined together to form a two-terminal Lewis base;

Any X group may be attached to the L group to form a mono-anionic 2-group.

Preferably, M is a Group 4 metal, such as zirconium or hafnium.

In a preferred embodiment, J is an aromatic substituted or unsubstituted hydrocarbyl (preferably hydrocarbyl) having 3 to 30 non-hydrogen atoms, preferably J is represented by the formula:

, 더 바람직하게는 J는

이다:

, More preferably J is

to be:

Expression ^{from, R 7, R 8, R} 9, R 10, R 10 ', R 11, R 11', R 12, R 14 , and E is as defined above and any two R groups (e.g., R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , R ¹⁰ and R ^11, etc.) Wherein the ring has 5, 6, 7, or 8 ring atoms (preferably 5 or 6 atoms) and the ring is saturated or unsaturated < RTI ID = 0.0 > (E.g., partially unsaturated or aromatic), preferably J is arylalkyl (e.g., arylmethyl, etc.) or dihydro-1H-indenyl, or tetrahydronaphthalenyl group.

In an embodiment of the present invention, J is selected from the following structures:

는 착물로의 연결을 나타낸다. In the formula,

Represents the connection to the complex.

In an embodiment of the present invention, E is carbon.

In an embodiment of the present invention, X is an alkyl (e.g., an alkyl group having 1 to 10 carbons such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof) An alkylsilane, a fluoride, a chloride, a bromide, an iodide, a triflate, a carboxylate, an amido (for example NMe ₂ ), or an alkylsulfonate.

In an embodiment of the present invention, L is an ether, an amine or a thioether.

In an embodiment of the present invention, R ⁷ and R ⁸ is bonded to form a 6-membered aromatic ring with the bonded R ⁷ R ⁸ group, which is -CH = CHCH = CH-.

In an embodiment of the present invention, R < ¹⁰ > and R ¹¹ are bonded to -CH ₂ CH ₂ - to form an original combination of the R ¹⁰ R ¹¹ group and 5 rings.

In an embodiment of the present invention, R < ¹⁰ > and R ¹¹ are bonded to -CH ₂ CH ₂ CH ₂ - to form a bond with R ¹⁰ R ¹¹ group and 6-membered ring.

In an embodiment of the present invention, R < ¹ > and R & R ¹³ is selected from the group consisting of F, Cl, Br, I, CF ₃ , NO ₂ , alkoxy, dialkylamino, aryl and alkyl groups having 1 to 10 carbons such as methyl, ethyl, propyl, butyl, pentyl, Lt; / RTI > may be independently selected from phenyl groups that are variously substituted with 0 to 5 substituents including, for example, methyl, ethyl, propyl, isopropyl, octyl, nonyl, decyl and isomers thereof.

In a preferred embodiment of the present invention, the quinolinyldiamido transition metal complex is represented by the above formula (II)

Wherein M is a Group 4 metal (preferably hafnium);

E is selected from carbon, silicon, or germanium (preferably carbon);

X is an alkyl, aryl, hydride, alkylsilane, fluoride, chloride, bromide, iodide, triflate, carboxylate, amido, alkoxo, or alkylsulfonate;

L is an ether, amine, or thioether;

R ¹ and R ¹³ is independently selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, and silyl groups (preferably aryl);

R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are independently selected from the group consisting of hydrogen, hydrocarbyl, alkoxy, , Substituted hydrocarbyl, halogen, and phosphino;

n is 1 or 2;

M is 0, 1, or 2;

n + M is 1 to 4;

Two X groups may be joined together to form a back ionic group;

Two L groups may be joined together to form a two-terminal Lewis base;

The X group may be attached to the L group to form a mono-anionic 2-group;

R ⁷ and R ⁸ may be joined to form a ring (preferably an aromatic ring, a 6-membered aromatic ring with the attached R ⁷ R ⁸ group wherein -CH = CHCH = CH-);

R < ¹⁰ & R ¹¹ is -CH ₂ is preferably coupled to the ring (CH ₂ - of the combined R ¹⁰ R ¹¹ A 5-membered ring of tapered rings, and a 6-membered ring with a -CH ₂ CH ₂ CH ₂ - bonded R ¹⁰ R ¹¹ group).

In embodiments of formulas I, II and III, R ⁴ , R ⁵ and R ⁶ are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, alkoxy, aryloxy, halogen, amino, , Wherein adjacent R groups (R < ⁴ > and R ⁵ and / or R ⁵ and R ⁶⁾ is which they are attached may form a substituted hydrocarbyl, unsubstituted hydrocarbyl, Beach cyclic a heterocyclic ring or a substituted cyclic hetero ring bond, the ring is 5, 6, 7, or 8 And the substitution on the ring may be combined to form an additional ring.

In embodiments of formulas I, II and III, R ⁷ _, R ⁸ _, R ⁹ and R ¹⁰ are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, alkoxy, halogen, amino, , Wherein adjacent R groups (R < ⁷ > and R ⁸ and / or R ⁹ and R ¹⁰ may be joined to form a saturated, substituted hydrocarbyl, unsubstituted hydrocarbyl, unsubstituted heterocyclic ring or substituted heterocyclic ring, said ring being optionally substituted with 5, 6, 7, Or have 8 ring carbon atoms and substitution on the ring may be combined to form an additional ring.

In embodiments of formulas I, II and III, R < ² > and R ³ are each, independently, it is selected from hydrogen, hydrocarbyl, and substituted hydrocarbyl, alkoxy, silyl, amino, aryloxy, halogen, and phosphino group consisting of, R ² and R ³ may be joined to form a saturated, substituted or unsubstituted hydrocarbyl ring, which ring has 4, 5, 6, or 7 ring carbon atoms, and the substitution on the ring is combined to form an additional ring Or R < ² > and R < ³ > may be combined to form a saturated heterocyclic ring, or a saturated substituted heterocyclic ring wherein the substituents on the rings may be joined to form additional rings.

In embodiments of formulas I, II, and III, R < ¹¹ > and R & R ¹² are each, independently, it is selected from hydrogen, hydrocarbyl, and substituted hydrocarbyl, alkoxy, silyl, amino, aryloxy, halogen, and phosphino group consisting of, R ^11, and R ¹² may be joined to form a saturated, substituted or unsubstituted hydrocarbyl ring, said ring having 4, 5, 6, or 7 ring carbon atoms and substitution on the ring being joined to form an additional ring Or R < ¹¹ > and R & R < ¹² > A saturated heterocyclic ring, or a saturated substituted heterocyclic ring wherein the substituents on the ring may be joined to form an additional ring, or R < ¹¹ > and R < ¹¹ & R ¹⁰ is Or a saturated saturated heterocyclic ring, or a saturated substituted heterocyclic ring wherein the substitution on the ring may be combined to form an additional ring.

In embodiments of formula I, II, or III, R < ¹ & R ¹³ is selected from the group consisting of F, Cl, Br, I, CF ₃ , NO ₂ , alkoxy, dialkylamino, aryl and alkyl groups having 1 to 10 carbons such as methyl, ethyl, propyl, butyl, pentyl, Lt; / RTI > may be independently selected from phenyl groups that are variously substituted with 0 to 5 substituents including, for example, methyl, ethyl, propyl, isopropyl, octyl, nonyl, decyl and isomers thereof.

In embodiments of formula II, preferred R ¹² -ER ¹¹ group is _{CH 2, CMe 2, SiMe 2} , SiEt 2, SiPr 2, SiBu 2, SiPh 2, Si ( aryl) _2, Si (alkyl) _2, CH (aryl ), CH (Ph), CH (alkyl), and CH (2-isopropylphenyl), wherein alkyl is a C ₁ to C ₄₀ alkyl group (preferably C ₁ to C ₂₀ alkyl, And the aryl is a C ₅ to C ₄₀ aryl group (preferably a C ₆ to C (preferably C ₆ to C ₁₀ aryl group) such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, ₂₀ aryl group, preferably phenyl or substituted phenyl, preferably phenyl, 2-isopropylphenyl, or 2-tert butylphenyl).

In an embodiment of formula III, R ¹¹ _, R ¹² _, R ⁹ , R ¹⁴ and R ¹⁰ are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, alkoxy, halogen, amino, Where adjacent R groups (R < ¹⁰ > and R & R < ¹⁴ >, and / or R < ¹¹ & R < ¹⁴ >, and / or R < ⁹ & R ¹⁰ may be joined to form a saturated, substituted hydrocarbyl, unsubstituted hydrocarbyl, unsubstituted heterocyclic ring or substituted heterocyclic ring, said ring being optionally substituted with 5, 6, 7, Or 8 ring carbon atoms, and the substitution on the ring may be combined to form an additional ring.

Preferably, the R group (i. E., Any R ² to R ¹⁴ ) and the other R groups mentioned below have 1 to 30, preferably 2 to 20 carbon atoms, especially 6 to 20 carbon atoms . Preferably, the R group (i.e., any of R ² to R ¹⁴⁾ and after the other R groups are independently hydrogen, methyl, ethyl, referred to, phenyl, isopropyl, butyl, trimethylsilyl, and -CH ₂ - Si (Me) < / RTI > ₃ .

In one possible embodiment, the quinolinyldiamide complexes may be reacted via the R group with one or more additional transition metal complexes in a manner to produce bimetallic, trivalent, or multi-metal complexes that can be used as catalyst components for olefin polymerization, Such as a quinolinyldiamide complex or a metallocene. The linker R group in such a complex preferably contains 1 to 30 carbon atoms.

Preferably, M is Ti, Zr, or Hf, E is carbon, and Zr or Hf based complexes are particularly preferred.

In any of the embodiments described herein, E is carbon and R < ¹² > R ¹¹ is selected from the group consisting of F, Cl, Br, I, CF ₃ , NO ₂ , alkoxy, dialkylamino, hydrocarbyl, and substituted hydrocarbyl having 1 to 10 carbons. , Phenyl group substituted with 3, 4, or 5 substituents.

In any of the embodiments described herein of the formula II or III, R ^11, and R ¹² is independently selected from hydrogen, methyl, ethyl, phenyl, isopropyl, isobutyl, -CH ₂ -Si (Me) ₃ , and trimethylsilyl.

R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, phenyl, cyclohexyl, fluoro, chloro, methoxy, ethoxy, phenoxy, is selected from -CH ₂ -Si (Me) _3, and trimethylsilyl.

In any of the embodiments described herein, R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are independently selected from the group consisting of hydrogen, hydrocarbyl, alkoxy, silyl, amino, Carbyl, and halogen.

In any of the embodiments described herein of formula III, R < ¹⁰ >, R < ¹¹ & R ¹⁴ is independently selected from hydrogen, methyl, ethyl, phenyl, isopropyl, isobutyl, -CH ₂ -Si (Me) ₃ , and trimethylsilyl.

In any of the embodiments described herein of formula I, II or III, each L is independently selected from Et ₂ O, MeOtBu, Et ₃ N, PhNMe ₂ , MePh ₂ N, tetrahydrofuran, and dimethyl sulfide do.

In any of the embodiments described herein of Formula I, II or III, each X is independently selected from the group consisting of methyl, benzyl, trimethylsilyl, neopentyl, ethyl, propyl, butyl, phenyl, hydrido, chloro, Is selected from bromo, iodo, dimethylamido, diethylamido, dipropylamido, and diisopropylamido.

In any of the embodiments described herein of formula I, II or III, R ¹ is selected from the group consisting of 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2,6-diisopropyl- Methylphenyl, 2,6-diethylphenyl, 2-ethyl-6-isopropylphenyl, 2,6-bis (3-pentyl) phenyl, 2,6-dicyclopentylphenyl, or 2,6-dicyclohexylphenyl to be.

In any of the embodiments described herein of Formula I, II, or III, R ¹³ is selected from the group consisting of phenyl, 2-methylphenyl, 2-ethylphenyl, 2-propylphenyl, 2,6-dimethylphenyl, Methylphenyl, 3,5-dimethylphenyl, 3,5-di-tert-butylphenyl, 4-fluorophenyl, 3-methylphenyl, 4-dimethylaminophenyl, or 2-phenylphenyl.

In any of the embodiments described herein of formula II, J is dihydro-1 H-indenyl and R ¹ is 2,6-dialkylphenyl or 2,4,6-trialkylphenyl.

In any of the embodiments described herein of formula I, II, or III, R ¹ is 2,6-diisopropylphenyl and R ¹³ is alkyl having 1, 2, 3, 4, 5, 6, or 7 carbon atoms Lt; / RTI >

In another embodiment of the present invention, various methods for synthesizing the complexes described herein are provided.

Ligand synthesis

The quinolinyldiamine ligands described herein are generally prepared in multiple steps. The key step in the synthesis of quinolinyldiamine ligands is the carbon-carbon bond coupling step shown in Scheme 1 below wherein Fragment 1 and Fragment 2 are bound together in a transition metal mediated reaction. In the specific example described herein, the coupling step involves the use of Pd (PPh _{3) 4,} but is useful for other transition metal catalyst (e.g., Ni or Cu-containing complexes) are also of this type of coupling reaction. In the specific examples described herein, the W ^* and Y ^* groups used are each a boronic acid ester and a halide. This selection is suitable for the Pd-mediated coupling step, but other airways may also be useful for the coupling reaction. Other possible W ^* and Y ^* groups of interest include alkali metals such as Li, alkaline earth metal halides such as MgBr, zinc halides such as ZnCl, zincate, halides, and triflates. In Scheme 1, R ¹ to R ¹³ and E is as described above.

One method for the preparation of transition metal quinolinyldiamide complexes is by reaction between a metal reactant containing anionic basic leaving group and quinolinyldiamine. Exemplary anionic basic leaving groups include dialkylamido, benzyl, phenyl, hydrido, and methyl. In this reaction, the role of the basic leaving group is to deprotonate the quinolinyldiamine ligand. Suitable metal reactants for this type of reaction include, but are not limited to, HfBn ₄ (Bn = CH ₂ Ph), ZrBn ₄ , TiBn ₄ , ZrBn ₂ Cl ₂ (OEt ₂ ), HfBn ₂ Cl _{2 (OEt 2) 2, Zr (} NMe 2) 2 Cl 2 ( _{dimethoxyethane), Hf (NMe 2) 2} Cl 2 ( _{dimethoxyethane), Hf (NMe 2) 4} , Zr (NMe 2) 4, and Hf (NEt ₂ ) ₄ . In a particular example presented herein, Hf (NMe ₂ ) ₄ is reacted with a quinolinyldiamine ligand at elevated temperature to form a quinolinyldiamine complex with the formation of two equivalents of dimethylamine, which is eliminated or removed before the quinolinyldiamide complex is isolated, Amide complexes.

A second method for the preparation of transition metal quinolinyldiamide complexes involves deprotonating a ligand by reacting an alkali metal or alkaline earth metal base (e.g., BuLi, EtMgBr) with a quinolinyldiamine ligand followed by a metal halide , HfCl ₄ , ZrCl ₄ ).

A quinolinyldiamide (QDA) metal complex containing a metal-halide, alkoxide, or amido leaving group can be alkylated by reaction with organolithium, Grignard, and organoaluminum reagents as shown in Scheme 2. In the alkylation reaction, the alkyl group is moved to the QDA metal center and the leaving group is removed. In Scheme 2, R ¹ to R ¹³ and E is as defined above and X ^* is a halide, alkoxide, or dialkylamido leaving group. A typically used reagent for the alkylation reaction is limited to, but include MeLi, MeMgBr, AlMe _3, AliBu _3, AlOct _3, and PhCH ₂ MgCl. Typically 2 to 20 molar equivalents of an alkylating reagent are added to the QDA complex. The alkylation is typically carried out in an etheric or hydrocarbon solvent or solvent mixture at a temperature typically in the range of from -80 占 폚 to 70 占 폚.

Schematic 2

Activator

After the complexes are synthesized, the catalyst system can be formed by combining the complex with the activator in any manner known in the literature, including supporting them for use in slurry or gas phase polymerization. The catalyst system can also be added to or generated from solution polymerization or bulk polymerization (in the monomer). The catalyst system typically comprises a complex as described above and an activator such as an alumoxane or a non-coordinating anion. Activation may be carried out using an alumoxane solution comprising modified MAO referred to herein as MMAO as well as methyl alumoxane referred to as MAO containing some high alkyl groups to improve solubility. Particularly useful MAOs can be purchased from Albemarle as a 10 wt% solution in toluene. The catalyst system used in the present invention preferably employs an activator selected from alumoxane such as methyl alumoxane, modified methyl alumoxane, ethyl alumoxane, isobutyl alumoxane, and the like. Mixtures of different alumoxanes and modified alumoxanes may also be used. It may be desirable to use visually transparent methyl alumoxane. Turbidated or gelled alumoxane can be filtered to produce a clear solution or transparent alumoxane can be torn off from the cloudy solution. Useful alumoxane is the modified methyl alumoxane (MMAO) cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A, registered under the patent number US 5,041,584).

When alumoxane or modified alumoxane is used, the molar ratio of catalyst complex: activator is from about 1: 3000 to 10: 1; Alternatively 1: 2000 to 10: 1; Alternatively from 1: 1000 to 10: 1; Alternatively 1: 500 to 1: 1; Alternatively from 1: 300 to 1: 1; Alternatively from 1: 200 to 1: 1; Alternatively from 1: 100 to 1: 1; Alternatively 1:50 to 1: 1; Alternatively from 1:10 to 1: 1. When the activator is an alumoxane (modified or unmodified), some embodiments select the maximum amount of active agent in excess of 5000 times the mole (per metal catalyst site) than the catalyst precursor. The preferred minimum activator: complex ratio is 1: 1 molar ratio.

Activation can also be carried out using non-coordinating anions, referred to as NCA of the type described in EP 277 003 A1 and EP 277 004 A1. NCA can be accomplished using, for example, [DMAH] ⁺ [NCA] ^- in which an N, N-dimethylanilinium (DMAH) cation reacts with a basic leaving group on the transition metal complex to form a transition metal complex cation and [NCA] ^- Ion pair. ≪ / RTI > The cation in the precursor may alternatively be trityl. Alternatively, the transition metal complex can react with a neutral NCA precursor such as B (C ₆ F ₅ ) ₃ , which extracts the anion group from the complex to form the activated species. Useful activators include N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (i.e., [PhNMe ₂ H] B (C ₆ F ₅ ) ₄ ) and N, N-dimethylanilinium tetrakis Naphthyl) borate, wherein Ph is phenyl and Me is methyl.

A non-coordinating anion (NCA) is defined as meaning an anion that does not coordinate to a catalytic metal cation or coordinates to a metal cation, but only to a weakly coordinating one. The term NCA is also defined to include multi-component NCA containing activators containing acidic cation groups and non-coordinating anions such as N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate. The term NCA is also defined to include neutral Lewis acids such as tris (pentafluorophenyl) boron which can react with the catalyst to form activated species by extraction of anionic groups. NCA is weakly coordinated such that neutral Lewis bases such as olefinic or acetylenically unsaturated monomers can displace it from the catalyst center. Any metal or metalloid capable of forming a compatible, weakly coordinating complex can be used or contained in the non-coordinating anion. Suitable metals include, but are not limited to, aluminum, gold, and platinum. Suitable sub-metals include, but are not limited to, boron, aluminum, phosphorus, and silicon. The term non-coordinating anion includes an ionic activator and a Lewis acid activator.

In addition, preferred activators useful herein include those described in US 7,247,687, column 169, line 50 to column 174, line 43, particularly column 172, line 24 to column 173, line 53.

Non-limiting examples of boron compounds that can be used as activating cocatalysts are those described as active (and specifically specifically enumerated) in US 8,658,556 and or US 6,211,105, incorporated herein by reference.

Preferably, the NCA containing the activator is at least one of N, N-dimethylanilinium tetra (perfluorophenyl) borate, N, N-dimethylanilinium tetrakis (perfluoronaphthyl) N, N-dimethylanilinium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, triphenylcarbenium tetrakis (perfluoronaphthyl) ) Borate, triphenylcarbenium tetrakis (perfluorobiphenyl) borate, triphenylcarbenium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, triphenylcarbenium tetrakis ) Borate, methyl bis (hydrogenated tallow) ammonium tetrakis (perfluorophenyl) borate, or methyl dialkylammonium tetrakis (perfluoroaryl) borate.

Preferred activators are N, N-dimethylanilinium tetrakis (perfluoronaphthyl) borate, N, N-dimethylanilinium tetrakis (perfluorobiphenyl) borate, N, N-dimethylanilinium tetrakis Bis (trifluoromethyl) phenyl) borate, triphenylcarbenium tetrakis (perfluoronaphthyl) borate, triphenylcarbenium tetra (3,5-bis tetrakis (perfluoro lobby phenyl) borate, triphenylcarbenium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, triphenylcarbenium tetrakis (perfluorophenyl) borate, [Ph ₃ C ⁺ ] [B (C ₆ F ₅ ) ₄ ^- ], [Me ₃ NH ⁺ ] [B (C ₆ F ₅ ) ₄ ^- ]; 1- (4- (tris (pentafluorophenyl) borate) -2,3,5,6-tetrafluorophenyl) pyrrolidinium; And tetrakis (pentafluorophenyl) borate, 4- (tris (pentafluorophenyl) borate) -2,3,5,6-tetrafluoropyridine.

In a preferred embodiment, the activator is selected from the group consisting of triarylcarbonium (such as triphenylcarbenium tetraphenyl borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis- (2,3,4,6 (Perfluorophenyl) borate, triphenylcarbenium tetrakis (perfluoronaphthyl) borate, triphenylcarbenium tetrakis (perfluorobiphenyl) borate, triphenylcarbenium tetrakis Trifluoromethyl) phenyl) borate).

In another embodiment, the activator is selected from the group consisting of one or more trialkylammonium tetrakis (pentafluorophenyl) borate, N, N-dialkyl anilinium tetrakis (pentafluorophenyl) Tetrakis (pentafluorophenyl) borate, trialkylammonium tetrakis- (2,3,4,6-tetrafluorophenyl) borate, N, N-dialkyl anilinium tetrakis - (2,3,4,6-tetrafluorophenyl) borate, trialkylammonium tetrakis (perfluoronaphthyl) borate, N, N-dialkyl anilinium tetrakis (perfluoronaphthyl) (Perfluorobiphenyl) borate, trialkylammonium tetrakis (perfluorobiphenyl) borate, N, N-dialkyl anilinium tetrakis (perfluorobiphenyl) Borate, N, N-dialkyl anilinium tetrakis (3,5-bis (trifluoromethyl) phenyl) Borate, N, N-dialkyl- (2,4,6-trimethylanilinium) tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, di- (i-propyl) ammonium tetrakis Fluorophenyl) borate, wherein alkyl is methyl, ethyl, propyl, n-butyl, sec-butyl, or t-butyl.

When NCA (such as an ionic or neutral stoichiometric activator) is used, the molar ratio of catalyst complex: activator is typically from 1:10 to 1: 1; 1:10 to 10: 1; 1:10 to 2: 1; 1:10 to 3: 1; 1:10 to 5: 1; 1: 2 to 1.2: 1; 1: 2 to 10: 1; 1: 2 to 2: 1; 1: 2 to 3: 1; 1: 2 to 5: 1; 1: 3 to 1.2: 1; 1: 3 to 10: 1; 1: 3 to 2: 1; 1: 3 to 3: 1; 1: 3 to 5: 1; 1: 5 to 1: 1; 1: 5 to 10: 1; 1: 5 to 2: 1; 1: 5 to 3: 1; 1: 5 to 5: 1; 1: 1 to 1: 1.2.

Alternatively, a co-activator may also be used in the present catalyst system. Complex: the active agent molar ratio is from 1: 100 to 100: 1; 1:75 to 75: 1; 1:50 to 50: 1; 1:25 to 25: 1; 1:15 to 15: 1; 1:10 to 10: 1; 1: 5 to 5: 1, 1: 2 to 2: 1; 1: 100 to 1: 1; 1:75 to 1: 1; 1:50 to 1: 1; 1:25 to 1: 1; 1:15 to 1: 1; 1:10 to 1: 1; 1: 5 to 1: 1; 1: 2 to 1: 1; 1: 10 to 2: 1.

Support

In some embodiments, the complexes described herein can be supported (with or without an activator) by any method effective to support other coordination catalyst systems, and the catalyst thus prepared can be used to oligomerize or polymerize olefins in a heterogeneous process ≪ / RTI > Catalyst precursors, activators, if necessary a co-activator, a suitable solvent, and a support may be added in any order or simultaneously. Typically, complexes and activators can be combined in a solvent to form a solution. The support is then added and the mixture is stirred for 1 minute to 10 hours. While the total solution volume may be greater than the pore volume of the support, some embodiments limit the total solution volume to less than that required to form the gel or slurry (about 90% to 400% of the pore volume, About 100-200%). After stirring, the residual solvent is removed under vacuum, typically at ambient temperature and for 10-16 hours. However, larger or less time and temperature are possible.

The complex may also be supported in the absence of the active agent; In this case, the activator (and, if necessary, the activator) is added to the liquid phase of the polymerization process. Additionally, two or more different complexes can be placed on the same support. Likewise, more than one activator or activator and a coactivator may be placed on the same support.

Suitable solid particle supports are typically composed of polymeric or refractory oxide materials, each of which is preferably porous. Any support material having an average particle size of preferably greater than 10 [mu] M is suitable for use in the present invention. Various embodiments select a porous support material such as talc, inorganic oxide, inorganic chloride, e.g., magnesium chloride, and a resin support material such as a polystyrene polyolefin or polymer compound or any other organic support material. Some embodiments select an inorganic oxide material as a support material comprising a Group 2, 3, 4, 5, 13 or Group 14 metal or metalloid oxide. Some embodiments select a catalyst support material to include silica, alumina, silica-alumina, and mixtures thereof. Other inorganic oxides may be provided alone or in combination with silica, alumina or silica-alumina. These are magnesia, titania, zirconia and the like. Lewis acid materials such as montmorillonite and similar clays can also be provided as supports. In this case, the support may optionally be doubled as the activator component, but additional activators may also be used.

The support material can be pretreated in any number of ways. For example, the inorganic oxide may be calcined, chemically treated with a dehydroxylating agent such as aluminum alkyl or the like, or both.

As noted above, polymeric carriers will also be suitable according to the present invention, see for example WO 95/15815 and US 5,427,991. The disclosed methods can be used to adsorb or absorb them on a polymeric support, in particular if they consist of porous particles, or chemically bond them in polymer chains or via functional groups, using the catalyst complexes, activators or catalyst systems of the present invention.

Useful supports typically have a surface area of 10-700 m ² / g, a pore volume of 0.1-4.0 cc / g and an average particle size of 10-500 μm. Some embodiments select a surface area of 50-500 m ² / g, a pore volume of 0.5-3.5 cc / g, or an average particle size of 20-200 μm. Other embodiments select a surface area of 100-400 m ² / g, a pore volume of 0.8-3.0 cc / g, and an average particle size of 30-100 μm. Useful supports typically have pore sizes of 10-1000 ANGSTROM, alternatively 50-500 ANGSTROM, or 75-350 ANGSTROM.

The catalytic complexes described herein generally comprise from 10 to 100 micromoles of complex per gram of solid support; Alternatively 20-80 micromoles of complex per gram of solid support; Or at a loading level of 40-60 micromoles of complex per gram of support. Larger or smaller values may be used provided the total amount of solid complex does not exceed the pore volume of the support.

polymerization

For purposes of the present invention and the claims, the term " continuous process " means a system operating without interruption or stoppage. For example, a continuous process to produce a polymer will be a process wherein the reactants are continuously introduced into one or more reactors and the polymer product is continuously recovered.

For purposes of the present invention and claims, solution polymerization means a polymerization process in which the polymer produced is dissolved in a liquid polymerization medium, such as an inert solvent or monomer (s), or a blend thereof, under polymerization conditions. Solution polymerization is typically uniform. Homogeneous polymerization is one in which the polymer product is dissolved in the polymerization medium. Such a system is preferably described in the literature [J. Vladimir Oliveira, C. Dariva, and J. C. Pinto, Ind. Eng, Chem. Res., 29, 2000, p. It is preferable not to be cloudy as described in [4627].

For purposes of the present invention and claims, bulk polymerization means a polymerization process in which the polymerized monomer and / or comonomer is used as a solvent or diluent with little or no inert solvent used as a solvent or diluent. Small fractions of inert solvent can be used as carriers for scavengers and catalysts. The bulk polymerization system contains less than 25 wt%, preferably less than 10 wt%, preferably less than 1 wt%, preferably less than 0 wt% of an inert solvent or diluent.

&Quot; Catalytic activity " is a measure of how many grams of polymer (P) are produced using a polymerization catalyst comprising W mmol of transition metal (M) over a period of time T; Can be expressed by the following equation: P / (T x W).

The catalytic complexes of the present invention described herein are useful in the polymerization of conventionally known unsaturated monomers to effect coordination catalyst-catalyzed polymerization, such as solution, slurry, gas phase and high pressure polymerization. Typically, one or more of the complexes described herein, one or more activators, and one or more monomers are contacted to produce a polymer. In certain embodiments, the complexes may be supported and will be particularly useful in known fixed bed, mobile bed, fluidized bed, slurry, solution or bulk mode of operation which are themselves carried out in single, series or parallel reactors.

One or more reactors in series or in parallel may be used in the present invention. The complexes, activators and, if desired, the activators can be delivered individually or as in-line just prior to the reactor or as a solution or slurry pumped into the reactor as a pre-activated activated solution or slurry. The polymerization is carried out in a single reactor operation in which monomers, comonomers, catalyst / activator / activator, selective scavenger, and optional modifier are continuously added to a single reactor, or a series reactor operation in which the components are added to each of two or more reactors connected in series Lt; / RTI > The catalyst component may be added to the first reactor in series. The catalyst component may also be added to both reactors by adding one component to the first reaction and adding another component to the other reactor. In one preferred embodiment, the complex is activated in the reactor in the presence of an olefin.

In a particularly preferred embodiment, the polymerization process is a continuous process.

The polymerization process used herein typically involves contacting the complexes described herein (and, optionally, activators) with one or more alkene monomers. For purposes of the present invention, alkenes are defined to include multiple alkenes (e. G., Dialkens) and alkenes having only one double bond. The polymerization can be homogeneous (solution or bulk polymerization) or heterogeneous (slurry-liquid diluent, or gas-gas diluent). In the case of heterogeneous slurry or gas phase polymerization, complexes and activators may be supported. Silica is useful herein as a support. Hydrogen may be useful in the practice of the present invention.

The present polymerization process is preferably carried out at a temperature of from about 30 캜 to about 200 캜, preferably from 60 캜 to 195 캜, preferably from 75 캜 to 190 캜, preferably from 80 캜 to 130 캜, ≪ / RTI >

The present polymerization process can be carried out at a pressure of 0.05 MPa to 1500 MPa. In a preferred embodiment, the pressure is from 1.7 MPa to 30 MPa, or in another embodiment, especially under supercritical conditions, the pressure is from 15 MPa to 1500 MPa.

Monomer

Monomers useful herein are those having from 2 to 20 carbon atoms, alternatively from 2 to 12 carbon atoms (preferably ethylene, propylene, butylene, pentene, hexene, heptene, octene, Also included are olefins having polyenes (such as dienes). Particularly preferred monomers include ethylene and mixtures of C ₂ to C ₁₀ alpha olefins such as ethylene-propylene, ethylene-hexene, ethylene-octene, propylene-hexene and the like.

The complexes described herein are also particularly effective in the polymerization of ethylene either alone or in combination with at least one other olefinically unsaturated monomer such as C ₃ to C ₂₀ alpha-olefins, and in particular C ₃ to C ₁₂ alpha-olefins. Likewise, the present complexes are also particularly effective in the polymerization of propylene either alone or in combination with at least one other olefinically unsaturated monomer such as ethylene or C ₄ to C ₂₀ alpha-olefins, and in particular C ₄ to C ₂₀ alpha-olefins to be. Examples of preferred? -Olefins are ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, , 3-methylpentene-1,3,5,5-trimethylhexene-1, and 5-ethylnonene-1.

In some embodiments, the monomer mixture may also include one or more dienes in an amount of up to 10% by weight, such as from 0.00001 to 1.0% by weight, such as from 0.002 to 0.5% by weight, such as from 0.003 to 0.2% by weight, based on the monomer mixture have. Non-limiting examples of useful dienes include cyclopentadiene, norbornadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, Hexadiene, 1,5-heptadiene, 1,6-heptadiene, 6-methyl-1,6-heptadiene, 1,7-octadiene, 1,9-decadiene, 1,9-dimethyl-1,9-decadiene.

Polymerization of ethylene and a propylene or propylene-rich copolymer is expected to produce a polymer in which crystalline isotactic polypropylene proceeds. This is expected to be due to the fact that the catalyst family has a seven-membered chelate ring which effectively makes the catalyst C ₁ symmetric (i.e., non-symmetric) in use.

Scavenger

In some embodiments, when the complexes described herein are used, the catalyst system will additionally comprise one or more scavenging compounds, particularly when they are immobilized on a support. As used herein, the term scavenging compound refers to a compound that removes polar impurities from the reaction environment. These impurities adversely affect the catalytic activity and stability. Typically, scavenging compounds are disclosed in US 5,153, 157; US 5,241,025; WO-A-91/09882; WO-A-94/03506; WO-A-93/14132; And an organometallic compound such as a Group 13 organometallic compound of WO 95/07941. Exemplary compounds include triethyl aluminum, triethyl borane, tri-iso - butyl aluminum, methyl alumoxane, iso - butyl alumoxane, and tri-n-octyl aluminum. These scavenging compounds with bulk or C ₆ -C ₂₀ linear hydrocarbyl substituents attached to a metal or metalloid center generally minimize negative interaction with the active catalyst. Examples include triethylaluminum, but more preferably, bulky compounds such as tri-iso-butyl aluminum, tri-iso-prenyl aluminum, and long-chain linear alkyl-substituted aluminum compounds, such as tri -n- hexyl aluminum, tri- n-octyl aluminum, or tri-n-dodecyl aluminum. When alumoxane is used as an activator, any excess required for activation will scaveng the impurities and additional scavenging compounds may be unnecessary. It is also possible to use alumoxane (methyl alumoxane), aluminum oxide (e.g. bis (diisobutyl aluminum) oxide) and modified alumoxane (e.g. MMAO-3A) as well as other active agents such as [Me ₂ HNPh] ⁺ [ pfp) ₄ ] ^- or B (pfp) ₃ (perfluorophenyl = pfp = C ₆ F ₅ ) in a scavenging amount.

Polymer product

The molecular weight of the polymers produced herein can be influenced by reactor conditions, including the presence of temperature, monomer concentration and pressure, chain terminator or chain-transfer agent, etc. However, The resulting homopolymer and copolymer product may be present in an amount of from about 1,000 to about 2,000,000 g / mol, alternatively from about 30,000 to about 600,000 g / mol, alternatively from about 100,000 to about 500,000 g / mol as determined by GPC (as described below) It may have a Mw of 500,000 g / mol.

The polymer produced herein has a density of at least 0.01 dg / min (preferably 0.1 to 50 dg / min, preferably 0.2 to 300 dg / min, preferably 0.1 to 1.5 dg / min, preferably 0.15 to 1.0 dg / min, preferably 0.15 to 0.8 dg / min) (ASTM 1238, 2.16 kg, 230 占 폚) at a melt flow rate (MFR). Alternatively, the polymer produced herein may have a melt flow rate (MFR) of at least 0.01 dg / min (preferably between 0.1 and 50 dg / min, preferably between 1 and 10 dg / min).

Preferred polymers prepared herein may be homopolymers or copolymers. In a preferred embodiment, the comonomer (s) is present at a maximum of 50 mol%, preferably 0.01 to 40 mol%, preferably 1 to 30 mol%, preferably 5 to 20 mol%.

In useful embodiments, the polymer produced is present in an amount of up to 10% by weight (preferably 0.00001 to 6.0% by weight, preferably 0.002 to 5.0% by weight, preferably 0.003 to 0.2% by weight) based on the weight of the copolymer (Preferably from 5 to 30, preferably from 5 to 25) and from 99 to 65 wt% of propylene (preferably from 95 to 70, preferably from 95 to 75, ). ≪ / RTI > Non-limiting examples of useful dienes include cyclopentadiene, norbornadiene, dicyclopentadiene, 5-ethylidene-2-norbornene ("ENB"), 5-vinyl- Hexadiene, 1,5-heptadiene, 1,6-heptadiene, 6-methyl-1,6-heptadiene, 1,7-octadiene, 7-octadiene, 1,9-decadiene, 1 and 9-methyl-1,9-decadiene.

In some embodiments herein, a multimode polyolefin composition is prepared wherein the GPC trace preferably has more than one peak or inflection point, wherein the multimodal polyolefin composition comprises a first polyolefin component and at least another polyolefin component having a molecular weight different from the first polyolefin component .

The term " multimodal " when used to describe a polymer or polymer composition means a " multimodal molecular weight distribution ", which refers to the absorbance versus residence time (seconds) (GPC) traces have more than one peak or at least one inflection point. The " inflection point " is the point at which the sign of the second derivative of the curve changes (e.g., negative to positive or vice versa). For example, a polyolefin composition comprising a first low molecular weight polymer component (e.g., a polymer having a Mw of 100,000 g / mol) and a second high molecular weight polymer component (e.g., a polymer having a Mw of 300,000 g / mol) quot; bimodal " polyolefin composition. Preferably, the Mw of the polymer or polymer composition is at least 10%, preferably at least 20%, preferably at least 50%, preferably at least 100%, preferably at least 200% different from each other. Likewise, in a preferred embodiment, the Mw of the polymer or polymer composition is between 10% and 10,000%, preferably between 20% and 1000%, preferably between 50% and 500%, preferably between 100% and 400% , Preferably 200% to 300%.

Unless otherwise indicated, the molecular weights of the monomers, i.e., the weight average molecular weight (Mw), the number average molecular weight (Mn), and the z average molecular weight (Mz) were measured using three polymer PLARGEL 10 mm (Waters Alliance 2000, SEC) equipped with a differential refractive index detector (DRI) equipped with a mixed-B column, as described in Macromolecules, 2001, Vol. 34, No. 19, pg. (GPC) as described in < RTI ID = 0.0 > 6812. < / RTI > The instrument is operated at a flow rate of 1.0 cm ³ / min and an injection volume of 300 μL. The various moving lines, columns and differential refractometer (DRI detector) are housed in an oven maintained at 145 占 폚. The polymer solution contained 0.75 to 1.5 mg / mL of filtered 1,2,4-trichlorobenzene (TCB) containing ~ 1000 ppm of butylated hydroxytoluene (BHT) with continuous shaking at 160 ° C for 2 hours ≪ / RTI > A sample of the polymer containing solution is injected with GPC and eluted using filtered 1,2,4-trichlorobenzene (TCB) containing ~ 1000 ppm BHT. The separation efficiency of the column set is corrected using a series of narrow MWD polystyrene standards that reflect the expected Mw range of the sample being analyzed and the exclusion limit of the column set. A calibration curve is generated using 17 individual polystyrene standards ranging from peak molecular weights (Mp) from 580 to 10,000,000 obtained from Polymer Laboratories (Amherst, MA). The flow rate is corrected for each run to provide a common peak position for the flow markers (considered as positive injection peaks) before determining the retention volume for each polystyrene standard. The flow marker peak position is used to calibrate the flow rate when analyzing the sample. The calibration curve (log (Mp) versus retention volume) is generated by recording the retention volume at the peak of the DRI signal for each PS standard and fitting this data set to a second order polynomial. The equivalent polyethylene molecular weights are determined using the Mark-Houwink coefficients shown in Table B below.

[Table B]

In a preferred embodiment, the homopolymer and copolymer product prepared by the present process have a molecular weight of from about 1,000 to about 2,000,000 g / mol, alternatively from about 30,000 to about 600,000 g / mol, alternatively from about 100,000 To about 500,000 g / mol and has a dual mode, preferably a dual mode, Mw / Mn.

In an embodiment of the present invention, the polymer produced is an ethylene polymer or a propylene polymer.

In an embodiment of the present invention, the polymer produced is a tactic polymer, preferably an isotactic or highly isotactic polymer. In an embodiment of the present invention, the polymer produced is an isotactic polypropylene, such as a high degree of isotactic polypropylene.

The term " isotactic polypropylene " (iPP) is defined as having at least 10% isotactic pentad. The term " highly isotactic polypropylene " is defined as having more than 50% isotactic pentads. The term " syndiotactic polypropylene " is defined as having a syndiotactic pentad of at least 10%. The term " random copolymer polypropylene " (RCP), also referred to as a propylene random copolymer, is defined as a copolymer of propylene and an olefin selected from ethylene and C ₄ to C ₈ alpha olefins in an amount of 1 to 10 wt%. Preferably, the isotactic polymer (such as iPP) has at least 20% (preferably at least 30%, preferably at least 40%) isotactic pentads. Polyolefins are " atactic ", also referred to as " amorphous ", when it has less than 10% isotactic pentad and syndiotactic pentad.

The polypropylene microstructure includes concentrations of isotactic and syndiotactic dyes ([m] and [r]), triads ([mm] and [rr]) and pentads ([mmmm] and [rrrr] And determined by ¹³ C-NMR spectroscopy. The designation " m " or " r " describes the stereochemistry of adjacent propylene group pairs, where " m " means meso and " r " The sample is dissolved in d ₂ -1,1,2,2-tetrachloroethane and the spectrum recorded at 125 ° C using a 100 MHz (or higher) NMR spectrometer. The polymer resonance peak is based on mmmm = 21.8 ppm. Calculations related to polymer characterization by NMR are described in FA Bovey in POLYMER CONFORMATION AND CONFIGURATION (Academic Press, New York 1969) and J. Randall in POLYMER SEQUENCE DETERMINATION, ¹³ C-NMR METHOD (Academic Press, New York, 1977) &Quot;

End use

Products made using the polymers produced herein can be used, for example, in the manufacture of molded products (such as containers and bottles such as household containers, industrial chemical containers, personal care bottles, medical containers, fuel tanks, Storages, toys, sheets, pipes and tubing) films, non-woven fabrics, and the like. It should be appreciated that the application list is merely exemplary and not intended to be limiting.

Experiment

¹ H NMR spectroscopic data were obtained at 250, 400, or 500 MHz using a solution prepared by dissolving approximately 10 mg of sample in either C ₆ D ₆ , CD ₂ Cl ₂ , CDCl ₃ , or D ₈ -toluene . The proposed chemical shifts (δ) are proportional to the residual propyl in deuterated solvents at 7.15, 5.32, 7.24 and 2.09 for C ₆ D ₆ , CD ₂ Cl ₂ , CDCl ₃ , and D ₈ -toluene, respectively. For purposes of the claims, 500 Mz and CD ₂ Cl ₂ are used.

A series of 2 - ((aminomethyl) phenyl) -8-anilinoquinoline ligands of hafnium complexes have been prepared and characterized. These complexes form an active olefin polymerization catalyst when combined with an activator such as N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate. The general structure of the precatalyst complex is shown below:

In the formula, the dashed line represents a selective bond and the solid line represents a bond. J group is a triatomic length bridge between quinoline and amido nitrogen (preferred J groups include arylmethyl and dihydro-1H-indenyl, and tetrahydronaphthalenyl groups); M is Hf; R ² to R ⁶ are H; X is NMe ₂ , or Me; n is 2; y is 0 and L is absent; R < ¹ > is 2,6-diisopropylphenyl; R ¹³ is 2-methylphenyl, 2,6-dimethylphenyl, or phenyl; R ¹² is H; R < ¹¹ > is H or forms a ring with R < ¹⁰ >; R ⁹ is H; R ¹⁰ is H or forms a ring with R ^11, R ^7, and R < ⁸ > are each H or combine together to form a six-membered aromatic ring.

A specific example of the quinolinyldiamine ligand produced is shown in Fig. A specific example of the quinolinyldiamido complex prepared is shown in Fig.

Ligand and Complex  synthesis

4,4,5,5- tetramethyl- 2- (2- methyl -1 -naphthyl ) -1,3,2 -dioxaborolane . 1,2-dibromoethane (about 0.3 ml) was added to magnesium turnings of 6.10 g (250 mmol) in 1000 mL of THF. The mixture was stirred for 10 min, then 55.3 g (250 mmol) of 1-bromo-2-methylnaphthalene was added with vigorous stirring, and the resulting mixture was stirred at room temperature for 3.5 hours. In addition, 46.5 g (250 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane were added in one go. The resulting mixture was stirred for 15 min and then poured into 1000 mL cold water. The product was extracted with 3 x 300 mL of ethyl acetate. The combined organic extracts were washed with water, brine, then dried and finally over MgSO _4, evaporated to dryness. The resulting white solid was washed with 2 x 75 mL of pentane and dried in vacuo. Yield 47.3 g (70%). _{^{1 H NMR (CDCl 3):}} δ 8.12 (m, 1H, 8-H), 7.77 (m, 1H, 5-H), 7.75 (d, J = 8.4 Hz, 1H, 4-H), 7.44 (m 3H), 2.63 (s, 3H, 2-Me), 1.48 (s, 3H) 12H, CMe ₂ CMe ₂ ).

2- [2- ( bromomethyl ) -1 -naphthyl ] -4,4,5,5- tetramethyl- 1,3,2 -dioxaborolane . 47.3 g (176 mmol) of 4,4,5,5-tetramethyl-2- (2-methyl-1-naphthyl) -1,3,2-dioxaborolane in 340 mL of carbon tetrachloride, 33.0 g 185 mmol) of N-bromosuccinimide, and 0.17 g of benzoyl peroxide was stirred at 75 < 0 > C for 14 hours. Further, the reaction mixture was cooled to room temperature, filtered through glass frit (G3), and the filtrate was evaporated to dryness. This procedure yielded 62.2 g (99%) of a beige solid. ¹ H NMR (CDCl ₃ ): δ 8.30 (m, 1H, 8-H), 7.84 (d, J = 8.3 Hz, 1H, (m, 3H, 3,6,7-H ), 4.96 (s, 2H, CH 2 Br), 1.51 (s, 12H, CMe 2 CMe 2).

2,6-dimethyl- N - {[1- (4,4,5,5- tetramethyl- 1,3,2 -dioxaborolan - 2 - yl ) -2 -naphthyl ] methyl} aniline. To a solution of 10.5 g (86.4 mmol) 2,6-dimethylaniline, 20.0 g (57.6 mmol) 2- [2- (bromomethyl) -1-naphthyl chloride in 400 mL N, N- dimethylformamide ] -4,4,5,5-tetramethyl-1,3,2-dioxaborolane, and 8.70 g (63.4 mmol) of K ₂ CO ₃ was stirred at 80 ° C for 12 hours. The resulting mixture was poured into 1000 mL of water. The crude product was extracted with 3 x 200 mL of ethyl acetate. The combined extracts MgSO ₄ Lt; / RTI > and then evaporated to dryness. Excess aniline was distilled off using a Kugelrohr apparatus. The product was isolated by flash chromatography on silica gel 60 (40-63 um; eluent: hexane-ethyl acetate = 20: 1, vol.). Yield 8.00 g (40%), yellow oil. _{^{1 H NMR (CDCl 3):}} δ 8.22 (d, J = 8.3 Hz, 1H), 7.79 (d, J = 8.3 Hz, 1H), 7.76 (d, J = 8.5 Hz, 1H), 7.47 (m, 2H 2H), 6.83 (s, 2H), 3.77 (br.s, 1H), 2.28 (d, J = (s, 6H), 1.44 (s, 12H).

2- methyl - N - {[1- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -2-naphthyl] methyl} aniline. 18.5 g (172 mmol) of 2-methylaniline in 500 mL of DMF, 40.0 g of 2- [2- (bromomethyl) -1-naphthyl] -4,4,5,5- ₃ , ₂ -dioxaborolane, and 17.5 g (126 mmol) of K ₂ CO ₃ was stirred at 80 ° C. for 12 hours under an argon atmosphere. The resulting mixture was poured into 1200 mL of water. The crude product was extracted with 3 x 200 mL of ethyl acetate. The combined organic extracts were Na ₂ SO ₄ Lt; / RTI > and then evaporated to dryness. The residue was recrystallized from a mixture of 300 mL of hexane and 20 mL of ethyl acetate. Yield 28.0 g (65%), yellow crystals. _{^{1 H NMR (CDCl 3):}} δ 8.20 (m, 1H), 7.84 (d, J = 8.5 Hz, 1H), 7.82 (m, 1H), 7.43-7.52 (m, 3H), 7.14 (m, 1H) , 7.06 (m, IH), 6.79 (m, IH), 6.68 (m, IH), 4.53 (s, 2H), 3.95 ).

8- (2,6 -diisopropylphenylamino ) quinolin-2 ( 1H ) -one. To a suspension of 5.63 g (140 mmol, 60 wt% in mineral oil) of NaH in 1000 mL anhydrous tetrahydrofuran (THF) was added 30.0 g (134 mmol) of 8-bromoquinolin-2 (1 H ) 0.0 > 0 C. < / RTI > The reaction mixture was then stirred at room temperature for 30 min. The resulting solution was cooled to 0 C and 20.2 g (134 mmol) of tert - butylchlorodimethylsilane were added in one portion. The resulting mixture was stirred for 30 min and then added to 1 L of water. The protected 8-bromoquinolin-2 ( 1H ) -one was extracted with 3 x 400 mL of diethyl ether. The combined extracts were Na ₂ SO ₄ Lt; / RTI > and then evaporated to dryness. This procedure yielded 45.2 g of protected 8-bromoquinolin-2 ( 1H ) -one (99% purity by GC / MS) as a dark red oil. To a solution of 27.7 mL (147 mmol) of 2,6-diisopropylaniline in 1500 mL anhydrous toluene was added 60.5 mL (147 mmol) of 2.5 M n-butyllithium in hexane at room temperature. The resulting suspension was heated to 100 < 0 > C and then cooled to room temperature. To the reaction mixture, 2.45 g (2.68 mmol) of Pd ₂ (dba) ₃ and 2.55 g (5.36 mmol) of 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl (XPhos) And 45.2 g (134 mmol) of protected 8-bromoquinolin-2 ( 1H ) -one were subsequently added. The resulting dark brown suspension was stirred at 60 < 0 > C until the lithium salt precipitate disappeared (approximately 30 minutes). The resulting dark red solution was quenched with 100 mL of water; The organic layer was separated, washed with Na ₂ SO ₄ ≪ / RTI > and then evaporated to dryness. The oil obtained was dissolved in a mixture of 1000 mL of dichloromethane and 500 mL of methanol and then 50 mL of 12 M hydrochloric acid was added. After stirring the reaction mixture at room temperature for 3 hours, it poured into 5% aqueous K ₂ CO ₃ in 2000 mL. The product was extracted with 3 x 700 mL of dichloromethane. The combined extracts were Na ₂ SO ₄ Lt; / RTI > and then evaporated to dryness. The resulting solid was triturated with 300 mL of hexane and then filtered off on glass frit (G3). Yield 34.1 g (79%), marsh-green solid. _{^{1 H NMR (CDCl 3):}} δ 13.29 (br.s, 1H), 7.80-7.81 (d, J = 9.5 Hz, 1H), 7.35-7.38 (m, 1H), 7.29-7.30 (m, 3H), J = 6.9 Hz, 2H), 1.25-1.26 (d, J = 9.5 Hz, 1H), 6.91-6.95 (m, 2H), 6.58-6.60 J = 6.9 Hz, 6H), 1.11-1.12 (d, J = 6.9 Hz, 6H).

2 -Chloro- N- (2,6 -diisopropylphenyl ) quinolin-8- amine . 15.0 g (46.9 mmol) of 8- (2,6-diisopropylphenylamino) quinolin-2 ( 1H ) -one was added to 250 mL of phosphorus oxychloride at once. The resulting suspension was stirred at 105 < 0 > C for 40 hours, then cooled to room temperature and poured into 4000 mL of crushed ice. The product was extracted with 3 x 400 mL of diethyl ether. The combined extracts were washed with K ₂ CO ₃ Lt; / RTI > and then evaporated to dryness. The resulting solid was triturated with 30 mL of cold hexane; The precipitate was filtered off on glass frit (G3) and then dried in vacuo. Yield 15.7 g (100%), yellowish green solid. _{^{1 H NMR (CDCl 3):}} δ 8.04-8.05 (d, J = 8.6 Hz, 1H), 7.38-7.39 (d, J = 8.5 Hz, 1H), 7.33-7.36 (m, 1H), 7.22-7.27 ( J = 7.8 Hz, 1H), 3.20 (sept, J = 6.9 Hz, 2H), 1.19-1.20 (d, J = , J = 6.9 Hz, 6H), 1.10-1.11 (d, J = 6.9 Hz, 6H).

7- Bromoindan- 1-ol. To a mixture of 100 g (746 mmol) of indan-1-ol, 250 mL (1.64 mol) of TMEDA, and 3000 mL of pentane cooled to -20 C was added 655 mL (1.64 mol) of 2.5 M ⁿ BuLi in hexane . The reaction mixture was then heated to reflux for 12 hours and then cooled to -80 占 폚. In addition, 225 mL (1.87 mol) of 1,2-dibromotetrafluoroethane was added and the resulting mixture was allowed to warm to room temperature. The mixture was stirred for 12 h and then 100 mL of water was added. The resulting mixture was diluted with 2 L of water and the organic layer was separated. The aqueous layer was extracted with 3 x 400 mL of toluene. The combined organic extracts were Na ₂ SO ₄ Lt; / RTI > and evaporated to dryness. The residue was distilled at 120 < 0 > C to 140 [deg.] C / 1 mbar using a Kugelrohr apparatus. The resulting yellow oil was dissolved in 50 mL of triethylamine and the solution was added to a solution of 49.0 mL (519 mmol) acetic anhydride in 70 mL triethylamine and 4.21 g (34.5 mmol) 4- (N, N-dimethyl Amino) pyridine < / RTI > (DMAP). The resulting mixture was stirred for 5 min, then 1 L of water was added and stirring continued for 12 h. The reaction mixture was then extracted with 3 x 200 mL of ethyl acetate. The combined organic extracts were washed with aqueous _{Na 2 CO 3, Na 2 SO} 4 Lt; / RTI > and evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um; eluent: hexane-ethyl acetate = 30: 1, vol.). The isolated ester was dissolved in 1000 mL of methanol and 50.5 g (900 mmol) of KOH was added. The mixture was refluxed for 3 hours, then cooled to room temperature and poured into 4000 mL of water. The title product was extracted with 3 x 300 mL of dichloromethane _. The combined organic extracts were Na ₂ SO ₄ Lt; / RTI > and evaporated to dryness. Yield 41.3 g (26%), white crystalline solid. _{^{1 H NMR (CDCl 3):}} δ 7.34 (d, J = 7.6 Hz, 1H, 6-H), 7.19 (d, J = 7.4 Hz, 1H, 4-H), 7.12 (dd, J = 7.6 Hz, 1H, 3-H), 5.33 (dd, J = 2.6 Hz, J = 6.9 Hz, 1H, 1-H), 3.18-3.26 3.09 (m, 2H, 3,3'-H), 2.73 (m, 2H, 2,2'-H).

7- Bromoindan- 1-one. To a solution of 37.9 g (177 mmol) of 7-bromoindan-1-ol in 3500 mL of dichloromethane was added 194 g (900 mmol) pyridinium chlorochromate. The resulting mixture was stirred at room temperature for 5 hours, then passed through a pad of silica gel 50 (40-63 um) (approx. 500 ml) and the eluent was evaporated to dryness. Yield 27.6 g (74%), white crystalline solid. _{^{1 H NMR (CDCl 3):}} δ 7.51 (m, 1H, 6-H), 7.36-7.42 (m, 2H, 4,5-H), 3.09 (m, 2H, 3,3'-H), 2.73 (m, 2H, 2,2 ' -H).

(7- bromo- 2,3 -dihydro- 1 H -inden-l-yl) phenylamine . To a stirred solution of 60 mL of toluene, 10.4 g (112 mmol) of the aniline of the TiCl ₄ 5.31 g (28.0 mmol) was added under an argon atmosphere at room temperature over a period of 30 min. The resulting mixture was stirred at 90 [deg.] C for 30 min and then 6.00 g (28.0 mmol) of 7-bromoanthan-1-one was added. It was then stirred for 10 min at 90 [deg.] C, poured into 500 mL of water, and the crude product was extracted with 3 x 100 mL of ethyl acetate. The combined organic extracts were Na ₂ SO ₄ Lt; / RTI > and then evaporated to dryness. The residue was recrystallized from 10 mL of ethyl acetate at -30 < 0 > C. Filtered to remove (G3) and the addition of NaBH ₃ CN and glacial acetic acid in 0.5 mL of dissolving the resulting crystalline solid dried under vacuum to 100 mL of methanol and then 2.70 g (42.9 mmol). The mixture was refluxed in an argon atmosphere for 3 h, then cooled to room temperature and evaporated to dryness. The residue was diluted with 200 mL of water and the crude product was extracted with 3 x 50 mL of ethyl acetate. The combined organic extracts were Na ₂ SO ₄ Lt; / RTI > and evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um; eluent: hexane-ethyl acetate-triethylamine = 100: 10: 1, vol.). Yield 5.50 g (68%), yellow oil. _{^{1 H NMR (CDCl 3):}} δ 7.38 (m, 1H), 7.22 (m, 3H), 7.15 (m, 1H), 6.75 (m, 1H), 6.69 (m, 2H), 4.94 (m, 1H) , 3.82 (br.s, 1H), 3.17-3.26 (m, 1H), 2.92-2.99 (m, 2H), 2.22-2.37 (m, 2H).

(7- Bromo- 2,3 -dihydro- 1 H -inden-1-yl) (2- methylphenyl ) amine . To a stirred solution of 2-methyl-aniline of 30.4 g (284 mmol) in toluene in 150 mL of TiCl ₄ in 13.5 g (71.0 mmol) at room temperature for 30 min it was added under an argon atmosphere. The resulting mixture was stirred at 90 [deg.] C for 30 min and then 15.0 g (71.0 mmol) of 7-bromoanthan-1-one was added. The mixture was stirred for 10 min at 90 < 0 > C, then poured into 500 mL of water and extracted with 3 x 200 mL of ethyl acetate. The combined organic extracts were separated, dried and evaporated dry over Na ₂ SO _4. The residue was recrystallized from 30 mL of ethyl acetate at -30 < 0 > C. The crystalline solid formed was filtered off (G3) and then dried in vacuo. This was then dissolved in 500 mL of methanol and then 8.34 g (132 mmol) of NaBH ₃ CN and 2.0 mL of glacial acetic acid were added. The resulting mixture was refluxed for 3 h, then cooled to room temperature, and evaporated to dryness. The residue was diluted with 200 mL of water and the crude product was extracted with 3 x 100 mL of ethyl acetate. The combined organic extracts were Na ₂ SO ₄ Lt; / RTI > and evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um; eluent: hexane-ethyl acetate-triethylamine = 100: 10: 1, vol.). Yield 17.4 g (81%), yellow crystalline solid. _{^{1 H NMR (CDCl 3):}} δ 7.41 (m, 1H), 7.26 (m, 1H), 7.16-7.22 (m, 2H), 7.09 (m, 1H), 6.78 (m, 1H), 6.72 (m, 1H), 4.97-7.98 (m, 1H), 3.70 (br.s, 1H), 3.20-3.29 (m, 1H), 2.96-3.01 s, 3H).

Phenyl [7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -2,3-dihydro-1 H -inden- 1 -yl] amine. To a solution of 2.50 g (8.70 mmol) of (7-bromo-2,3-dihydro- 1H -inden-l-yl) phenylamine in 50 mL of THF was added 3.50 mL (8.70 mmol) n-BuLi was added at-80 C under an argon atmosphere. The reaction mixture was then stirred at this temperature for 1 hour. Further, 11.1 mL (17.8 mmol) of 1.7 M t-BuLi in pentane was added and the reaction mixture was stirred for 1 h. Then 3.23 g (17.4 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane were added. The cooling bath was then removed and the resulting mixture was stirred at room temperature for 1 hour. To the resulting mixture was added 10 mL of water and the resulting mixture was evaporated to dryness. The residue was diluted with 200 mL of water and the title product was extracted with 3 x 50 mL of ethyl acetate. The combined organic extracts were Na ₂ SO ₄ Lt; / RTI > and evaporated to dryness. Yield 2.80 g (96%), pale yellow oil. _{^{1 H NMR (CDCl 3):}} δ 7.63 (m, 1H), 7.37-7.38 (m, 1H), 7.27-7.30 (m, 1H), 7.18 (m, 2H), 6.65-6.74 (m, 3H), (M, 1H), 1.20 (s, 6H), 2.20-2. 21 ), 1.12 (s, 6H).

(2-methylphenyl) [7- (4,4,5,5-tetramethyl-1,3,2 dioxaborolan-2-yl) -2,3-dihydroxy -1 H - inden -1 -Yl] amine. 17.4 g (57.6 mmol) of in 350 mL THF (7- bromo-2,3-dihydro -1 H - inden-1-yl) (2,6-dimethylphenyl) 23.0 mL of hexane to a solution of the amine ( 57.6 mmol) of 2.5M n-BuLi was added at -80 < 0 > C under an argon atmosphere. The reaction mixture was then stirred at this temperature for 1 hour. Further, 74.0 mL (118 mmol) of 1.7 M t-BuLi in pentane was added and the reaction mixture was stirred for 1 hour. Then, 21.4 g (115 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added. The cooling bath was then removed and the resulting mixture was stirred for 1 hour at room temperature. Then, 10 mL of water was added and the mixture was evaporated to dryness. The residue was diluted with 200 mL of water and the title product was extracted with 3 x 50 mL of ethyl acetate. The combined organic extracts were Na ₂ SO ₄ Drying and then And evaporated to dryness. Yield 17.1 g (85%), pale yellow oil. _{^{1 H NMR (CDCl 3):}} δ 7.72 (d, J = 7.1 Hz, 1H), 7.45 (d, J = 7.3 Hz, 1H), 7.35 (dd, J = 7.1 Hz, J = 7.3 Hz, 1H), 1H), 7.29 (m, 1H), 7.08 (d, J = 7.1 Hz, 1H), 6.90 2H), 2.22-2.27 (m, 1H), 2.06 (s, 3H), 1.23 (m, , ≪ / RTI > 6H), 1.14 (s, 6H).

N- (2,6- diisopropylphenyl) -2- {2 - [(o- tolyl) methyl] naphthalene-1-yl} quinolin-8-amine (Q1-H _2). In 50 mL of dioxane in 540 mg (1.59 mmol) 2- chloro -N- methyl 2- (2,6-diisopropylphenyl) 476 mg (1.28 mmol) to a solution of quinoline-8-amine - N - {[1- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -2-naphthyl] methyl} aniline. Then 1.30 g (3.98 mmol) of cesium carbonate and 15 mL of water were added subsequently. Purge the resulting mixture with argon, which was then added Pd (PPh _{3) 4} in 92 mg (0.08 mmol). The mixture was stirred for 2 h at 90 < 0 > C and then cooled to room temperature. Was added and the resulting two-phase mixture of 100 mL of hexane, and the organic layer was separated, washed with brine, Na ₂ SO ₄ Lt; / RTI > and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um; eluent: hexane-ethyl acetate-triethylamine = 100: 5: 1, vol.) And then recrystallized with 25 mL of hexane. Yield 650 mg (93%), yellow powder. _{^{1 H NMR (CDCl 3):}} δ 8.22-8.23 (d, J = 8.2 Hz, 1H), 7.95-7.96 (d, J = 8.5 Hz, 1H), 7.91-7.93 (d, J = 8.0 Hz, 1H) , 7.73-7.75 (d, J = 8.5 Hz, 1H), 7.58-7.61 (m, 3H), 7.50 (t, J = 7.6 Hz, 1H) 2H), 7.22-7.25 (m, 2H), 7.15-7.17 (d, J = 8.0Hz, 1H), 6.98-7.01 2H), 3.82 (br.s, 1H), 3.19-3.30 (m, 2H), 6.51-6.52 (d, J = 7.8 Hz, (m, 2H), 2.05 (s, 3H), 1.07 - 1.14 (m, 12H).

N- (2,6-diisopropylphenyl) -2- {2 - [(2,6-dimethylphenyl) methyl] naphthalene-1-yl} quinolin-8-amine (Q2-H _2). To a solution of 1.95 g (5.73 mmol) of 2-chloro-N- (2,6-diisopropylphenyl) quinolin-8-amine in 125 mL of dioxane was added 2.00 g (5.15 mmol) N - {[1- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -2-naphthyl] methyl} aniline. 4.70 g (14.4 mmol) of cesium carbonate and 50 mL of water were then added subsequently. Purge the resulting mixture with argon and then added to ₄ Pd (PPh ₃₎ of 330 mg (0.30 mmol). The mixture was stirred for 2 hours at 90 < 0 > C, then cooled to room temperature. To the resulting two-phase mixture was added 200 mL of hexane. The organic layer was separated, washed with brine, dried over Na ₂ SO _4, and was then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um; eluent: hexane-ethyl acetate-triethylamine = 100: 5: 1, vol.) And then recrystallized from 50 mL of hexane. Yield 1.54 g (48%), yellow powder. _{^{1 H NMR (CDCl 3):}} δ 8.19-8.21 (d, J = 8.3 Hz, 1H), 7.91-7.94 (m, 2H), 7.61-7.63 (d, J = 8.5 Hz, 1H), 7.47-7.56 ( (m, 2H), 7.17-7.22 (m, 3H), 6.87-6.89 (d, J = 7.5 Hz, 2H), 6.76-6.80 2H), 3.00 (s, 2H), 3.39 (br.s, 1H), 3.15-3.24 (m, 2H), 2.00 6H), 1.10-1.12 (d, J = 6.5 Hz, 3H), 1.07-1.08 (d, J = 6.9 Hz, 3H), 1.03-1.04 (d, J = 6.7 Hz, 3H), 0.96-0.98 , ≪ / RTI > J = 6.3 Hz, 3H).

N- (2,6- diisopropylphenyl) -2- [3- (phenylamino) -2,3-dihydro -1 H - inden-4-yl] quinolin-8-amine (Q3 _H-2) . To a solution of 4.63 g (13.6 mmol) of 2-chloro-N- (2,6-diisopropylphenyl) quinolin-8-amine in 250 mL dioxane was added 4.10 g (12.3 mmol) phenyl [7- , 4,5,5- tetramethyl-1,3,2 dioxaborolan-2-yl) -2,3-dihydro -1 H - inden-1-yl] was added to the amine. 11.1 g (34.0 mmol) of cesium carbonate and 80 mL of water were subsequently added. Purge the resulting mixture with argon and then added to ₄ Pd (PPh ₃₎ of 790 mg (0.68 mmol). The mixture was stirred for 2 hours at 90 < 0 > C, then cooled to room temperature. Was added to 300 mL of hexane to the resulting two-phase mixture, and the organic layer was separated, washed with brine, Na ₂ SO ₄ ≪ / RTI > and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um; eluent: hexane-ethyl acetate-triethylamine = 100: 5: 1, vol.) And then recrystallized from 150 mL of hexane. Yield 2.15 g (34%), yellow powder. _{^{1 H NMR (CDCl 3):}} δ 8.01-8.03 (d, J = 8.5 Hz, 1H), 7.87-7.89 (d, J = 8.5 Hz, 1H), 7.77-7.78 (d, J = 7.3 Hz, 1H) , 7.66 (br.s, 1H), 7.41-7.49 (m, 2H), 7.32-7.36 (m, 1H), 7.25-7.28 J = 7.7 Hz, 1 H), 5.40-7.09 (m, 3H), 6.63 (t, J = 7.3 Hz, 2H), 1.13-1.23 (m, 12H (m, 1H), 2.48-3. ).

N- (2,6- Diisopropylphenyl ) -2- [3- (o-tolyl Amino ) -2,3-dihydro-1 H 4-yl] quinolin-8-amine (Q4-H ₂ ).To a solution of 3.94 g (11.6 mmol) of 2-chloro-N- (2,6-diisopropylphenyl) quinolin-8-amine in 250 mL dioxane was added 3.66 g (10.5 mmol) 7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -2,3-dihydro-HLt; / RTI > amine was added. 9.50 g (29.0 mmol) of cesium carbonate and 80 mL of water were then added subsequently. The resulting mixture was purged with argon and then 670 mg (0.58 mmol) Pd (PPh₃)₄Was added. this The mixture was stirred at 90 < 0 > C for 2 hours, then cooled to room temperature. To the resulting two-phase mixture was added 300 mL of hexane. The hexane layer was separated, washed with brine, dried over Na₂SO₄ ≪ / RTI > and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um; eluent: hexane-ethyl acetate-triethylamine = 100: 5: 1, vol.) And then recrystallized with 100 mL of hexane. Yield 3.80 g (69%), yellow powder.^One1 H NMR (CDCl 3₃):δ (M, 2H), 7.18-7.37 (m, 2H), 7.95-7.97 (d, J = 8.7 Hz, 1H), 7.76-7.78 J = 8.1 Hz, 1H), 6.90-6.92 (d, J = 7.1 Hz, 1H), 6.68-6.70 (d, J = 7.9 Hz, 1 H), 6.59 (t, J = 7.1 Hz, 1 H), 6.24 - 6.26 (d, J = 6.9 Hz, 1 H), 5.48 - (M, 1H), 1.67 (s, 3H), 1.22-2.27 (m, J = 6.7 Hz, 3H), 1.17-1.19 (d, J = 6.7 Hz, 3H), 1.14-1.16 (d, J = , 3H).

Complex _{(Q1) Hf (NMe 2)} 2. It was added and the mixture in decane (12 mL) the _{Q1-H 2 (0.304 g,} 0.553 mmol) , and _{Hf (NMe 2) 4 (0.206} g, 0.581 mmol) was warmed for 1 hour to 165 ℃. The volatiles were removed by evaporation to give a red solid which was washed with pentane (5 mL) and dried. Yield: 0.37 g, 82%.

Complex (Q1) HfMe _{2 .} It was added to toluene (8 mL) to _{(Q1) Hf (NMe 2)} 2 (0.370 g, 0.454 mmol) to form a solution. Trimethylaluminum (0.294 g, 4.08 mmol) dissolved in toluene (2 mL) was added and the mixture was warmed to 60 < 0 > C. After 3 hours the volatiles were evaporated using a nitrogen stream. The red solid was washed with pentane (5 mL) and dried. Yield: 0.2 g, 58%.

Complex _{(Q2) Hf (NMe 2)} 2. Hf (NMe ₂₎ of 134 mg (0.37 mmol) to a solution of Q2 _H-2 of 207 mg (0.36 mmol) in 10 mL of decane was added to _4. The suspension was heated to 165 DEG C to dissolve the solid. The temperature was lowered to 100 < 0 > C and stirred for 12 hours. The solvent was evaporated until a solid formed and then cooled to room temperature. The resulting solid was filtered off and washed with pentane. Yield 122 mg (40%), red powder.

Complex (Q2) HfMe _{2 .} AlMe ₃ of the _{(Q2) Hf (NMe 2)} 2 172 mg (2.39 mmol) of 20% by weight solution in toluene to a solution of toluene 219 mg (0.26 mmol) of 5 mL were added. The solution was stirred at 60 < 0 > C for 5 hours. The solvent was then evaporated to near dryness and 4 mL of pentane was added. The resulting red solid was filtered and washed with pentane. Yield 103 mg (50%), red powder. ^{_{1 H NMR (C 6 D 6}} ): δ 7.73 (d, 1H), 7.62 (m, 2H), 7.51 (d, 1H), 7.34-7.05 (m, 9H), 6.96-6.90 (m, 2H), (D, 1H), 3.81 (d, 1H), 2.81 (d, 1H) (s, 3H), 1.21 (m, 6H), 0.914 (t, 6H), 0.06 (s, 3H), 0.36 (s, 3H).

Complex _{(Q3) Hf (NMe 2)} 2. The Hf (NMe _{2) 4} was added 164 mg (0.46 mmol) to a solution of Q3-H ₂ of 221 mg (0.43 mmol) of decane of 10 ml. The suspension was heated to 165 < 0 > C and stirred for 10 min. The heating was reduced to 100 < 0 > C and stirred for an additional 5 min, at which time a red solid was visible. The suspension was cooled to room temperature and the solid was filtered off and washed with pentane. Yield 225 mg (76%), red powder.

Complex (Q3) HfMe _2. the AlMe ₃ was added (Q3) Hf 88.0 mg (1.22 mmol) of (NMe ₂₎ 20% by weight solution in toluene to a solution of ₂ in toluene of 101 mg (0.13 mmol) in 3 ml. The solution was stirred at 50 < 0 > C for 1 hour. The solvent was then evaporated to near dryness and 4 mL of pentane was added. The resulting red solid was filtered and washed with pentane. Yield 45.0 mg (48%), red powder. ^{_{1 H NMR (C 6 D 6}} ): δ 7.67 (d, 1H), 7.34-6.86 (m, 13H), 6.75 (d, 1H), 6.19 (d, 1H), 4.84 (d, 1H), 3.68 ( 1H), 1.34 (d, 3H), 1.07 (q, 1H), 1.45 (q, , 3H), 0.92 (d, 3H), 0.78 (d, 3H), 0.34 (s, 3H), -0.05 (s, 3H).

Complex _{(Q4) Hf (NMe 2)} 2. Hf (NMe ₂₎ of 148 mg (0.41 mmol) to a solution of Q4-H ₂ of 211 mg (0.40 mmol) in 10 mL of decane was added to _4. The suspension was heated to 165 DEG C to dissolve the solid. The temperature was lowered to 100 < 0 > C and stirred for 12 hours. The solvent was evaporated until the solid started to form and cooled to room temperature. The resulting solid was filtered off and washed with pentane. Yield, 233 mg (73%), red powder.

Complex (Q4) HfMe ₂ . Of toluene 101 mg (0.13 mmol) in 5 ml (Q4) Hf (NMe 2) ₃ was added to AlMe of 82.0 mg (1.13 mmol) of 20% solution by weight of toluene to the solution of _2. The solution was stirred at 55 < 0 > C for 2 hours. The solvent was then evaporated to near dryness and 4 ml of pentane was added. The resulting red solid was filtered and washed with pentane. Yield 38.4 mg (41%), red powder. ^& Lt; ¹ > H NMR spectroscopic data show a broad resonance suggesting the presence of rotational isomers interconverting on a time scale of data acquisition.

8- Bromo- 1,2,3,4- tetrahydronaphthalen- l-ol . A solution of 78.5 g (530 mmol) of 1,2,3,4-tetrahydronaphthalen-1-ol, 160 mL (1.06 mol) of N, N, N ', N'-tetramethylethylenediamine, To the cooled mixture of 3000 mL of pentane was added dropwise 435 mL (1.09 mol) of 2.5 M ⁿ BuLi in hexane. The resulting mixture was refluxed for 12 h, then cooled to -80 < 0 > C and 160 mL (1.33 mol) of 1,2-dibromotetrafluoroethane were added. The resulting mixture was allowed to warm to room temperature and then stirred at this temperature for 12 h. Then, 100 mL of water was added. The resulting mixture was diluted with 2000 mL of water and the organic layer was separated. The aqueous layer was extracted with 3 x 400 mL of toluene. The combined organic extracts were evaporated to dryness and then dried over Na ₂ SO _4. The residue was distilled using a Cougelor apparatus, bp 150-160 [deg.] C / 1 mbar. The resulting yellow oil was dissolved in 100 mL of triethylamine and the solution was added dropwise to a stirred solution of 71.0 mL (750 mmol) acetic anhydride and 3.00 g (25.0 mmol) DMAP in 105 mL triethylamine . The formed mixture was stirred for 5 min, then 1000 mL of water was added and the resulting mixture was stirred for 12 h. The reaction mixture was then extracted with 3 x 200 mL of ethyl acetate. The combined organic extracts were washed with aqueous Na ₂ CO _3, dried over Na ₂ SO _4, and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-ethyl acetate = 30: 1, vol.). The isolated ester was dissolved in 1500 mL of methanol, 81.0 g (1.45 mol) of KOH was added, and the resulting mixture was heated to reflux for 3 h. The reaction mixture was then cooled to room temperature and poured into 4000 mL of water. The title product was extracted with 3 x 300 mL of dichloromethane _. The combined organic extracts were Na ₂ SO ₄ Lt; / RTI > and then evaporated to dryness. Yield 56.0 g (47%), white crystalline solid. _{^{1 H NMR (CDCl 3):}} δ 7.38-7.41 (m, 1H, 7-H); 7.03-7.10 (m, 2H, 5, 6-H); (M, 1H, 4'4-H), 2.56 (br.s, 1 H), 2.81-2.87 1H, OH), 2.17-2.21 (m, 2H, 2,2'-H), 1.74-1.79 (m, 2H, 3,3'-H).

8- Bromo- 3,4 -dihydronaphthalen- l (2 & apos ; H ) -one . To a solution of 56.0 g (250 mmol) of 8-bromo-1,2,3,4-tetrahydronaphthalen-1-ol in 3500 mL of dichloromethane was added 265 g (1.23 mol) of pyridinium chlorochromate (PCC) Was added. The resulting mixture was stirred at room temperature for 5 h, then passed through a pad of silica gel 60 (500 mL; 40-63 um), and finally evaporated to dryness. Yield 47.6 g (88%), colorless solid. _{^{1 H NMR (CDCl 3):}} δ 7.53 (m, 1H, 7-H); 7.18-7.22 (m, 2H, 5, 6-H); 2.95 (t, J = 6.1 Hz, 2H, 4,4 '-H); 2.67 (t, J = 6.6 Hz, 2H, 2,2 '-H); 2.08 (quint, J = 6.1 Hz, J = 6.6 Hz, 2H, 3,3'-H).

(8- bromo- 1,2,3,4- tetrahydronaphthalen- 1-yl) phenylamine . To a stirred solution of 140 mL of toluene, 21.6 g (232 mmol) of the aniline of the TiCl ₄ 10.93 g (57.6 mmol) was added under an argon atmosphere at room temperature over a period of 30 min. The resulting mixture was stirred at 90 [deg.] C for 30 min and then 13.1 g (57.6 mmol) of 8-bromo-3,4-dihydronaphthalene-1 ( 2H ) -one was added. The mixture was stirred for 10 min at 90 < 0 > C, then cooled to room temperature, and poured into 500 mL of water. The product was extracted with 3 x 50 mL of ethyl acetate. The combined organic extracts were Na ₂ SO ₄ , Evaporated to dryness and the residue was recrystallized from 10 mL of ethyl acetate. Dissolving the crystalline solid obtained in 200 mL of methanol, was added NaBH ₃ CN and acetic acid in 3 mL of 7.43 g (118 mmol) in an argon atmosphere. The mixture was heated to reflux for 3 h, then cooled to room temperature, and evaporated to dryness. The residue was diluted with 200 mL of water and the crude product was extracted with 3 x 100 mL of ethyl acetate. The combined organic extracts were Na ₂ SO ₄ Lt; / RTI > and evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-ethyl acetate-triethylamine = 100: 10: 1, vol.). Yield: 13.0 g (75%), yellow oil. Anal. Calcd for C ₁₆ H ₁₆ BrN: C, 63.59; H, 5.34; N, 4.63. Found: C, 63.82; H, 5.59; N, 4.49. _{^{1 H NMR (CDCl 3):}} δ 7.44 (m, 1H), 7.21 (m, 2H), 7.05-7.11 (m, 2H), 6.68-6.73 (m, 3H), 4.74 (m, 1H), 3.68 ( 1H), 2.84-2.89 (m, 1H), 2.70-2.79 (m, 1H), 2.28-2.32 , ≪ / RTI > 1H), 1.58-1.66 (m, 1H).

N -phenyl-8- (4,4,5,5-tetramethyl - 1,3,2 -dioxaborolan -2- yl ) -1,2,3,4-tetrahydronaphthalen- 1 -amine. To a solution of 13.0 g (43.2 mmol) (8-bromo-1,2,3,4-tetrahydronaphthalen-l-yl) phenylamine in 250 mL THF was added 17.2 mL (43.0 mmol) 2.5 M ⁿ BuLi At -80 < 0 > C. Further, the mixture was stirred at this temperature for 1 h and 56.0 mL (90.3 mmol) of 1.6 M ^t BuLi in pentane was added. The resulting mixture was stirred at the same temperature for 1 h. Then 16.7 g (90.0 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane were added. The cooling bath was then removed and the resulting mixture was stirred for 1 h at room temperature. Finally, 10 mL of water was added and the resulting mixture was evaporated to dryness. The residue was diluted with 200 mL of water and the crude product was extracted with 3 x 100 mL of ethyl acetate. The combined organic extracts were Na ₂ SO ₄ Lt; / RTI > and then evaporated to dryness. Yield 15.0 g (98%), yellow oil. Anal. Calcd for C ₂₂ H ₂₈ BNO ₂ : C 75.65; H 8.08; N 4.01. Found: C 75.99; H 8.32; N 3.79. _{^{1 H NMR (CDCl 3):}} δ 7.59 (m, 1H), 7.18-7.23 (m, 4H), 6.71-6.74 (m, 3H), 5.25 (m, 1H), 3.87 (br.s, 1H, NH ), 2.76-2.90 (m, 2H), 2.12-2.16 (m, 1H), 1.75-1.92 (m, 3H), 1.16 (s, 6H), 1.10 (s, 6H).

2- (8-anilino-5,6,7,8-tetrahydronaphthalene-1-yl) - N - (2,6- diisopropyl-phenyl) quinolin-8-amine (Q5-H _2). In 700 mL 13.8 g (41.0 mmol) of 1,4-dioxane, of 2-Chloro - N - (2,6- diisopropylphenyl) of quinolin-8-amine 15.0 g (43.0 mmol) to a solution of N - Phenyl-8- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,2,3,4-tetrahydronaphthalen- 1 -amine, 35.0 g (107 mmol) of cesium carbonate and 400 mL of water. The resulting mixture was purged with argon for 10 min, followed by addition of 2.48 g Pd (PPh ₃₎ a (2.15 mmol) _4. The resulting mixture was stirred at 90 < 0 > C for 2 h, then cooled to room temperature. To the resulting two-phase mixture was added 700 mL of n -hexane. The organic layer was separated, washed with brine, Na ₂ SO ₄ ≪ / RTI > and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-ethyl acetate-triethylamine = 100: 5: 1, vol.) And then recrystallized with 150 mL n -hexane . Yield 15.1 g (70%), yellow powder. Anal. Calcd for C ₃₇ H ₃₉ N ₃ : C 84.53; H 7.48; N 7.99. Found: C 84.60; H 7.56; N 7.84. _{^{1 H NMR (CDCl 3):}} δ 7.85-7.87 (d, J = 7.98 Hz, 1H), 7.56 (br.s, 1H), 7.43-7.45 (d, J = 8.43 Hz, 1H), 7.21-7.38 ( (t, J = 7.39 Hz, 1H), 6.74 (t, J = 7.99 Hz, 1H) 2H), 2.83-2.99 (m, 2H), 3.60-3. 49 (m, 2H) 2.10-2.13 (m, 1H), 1.77-1.92 (m, 3H), 1.13-1.32 (m, 12H).

Complex (Q5) HfMe _2. benzene (50 mL) to form a clear orange solution was added to the _{Q5-H 2 (2.21 g,} 4.20 mmol) and _{Hf (NMe 2) 4 (1.58} g, 4.45 mmol). The mixture was heated to reflux for 16 hours to form a clear red-orange solution. Most of the volatiles were removed by evaporation under a stream of nitrogen to give a concentrated red solution (ca. 5 mL) warmed to 40 < 0 > C. Hexane (30 mL) was then added and the mixture was stirred to form an orange crystalline solid. The slurry was cooled to-40 C for 30 min and then the solid was collected by filtration and washed with additional cold hexanes (2 x 10 mL). (Q5) Hf (NMe ₂₎ and dried under reduced pressure and the resulting orange solid of _{2 (2.90 g, 3.67 mmol,} 87.4% yield). This solid was dissolved in toluene (25 mL) and Me ₃ Al (12.8 mL, 25.6 mmol) was added. The mixture was warmed to 40 < 0 > C for 1 hour and then evaporated under a stream of nitrogen. The crude product (2.54 g) was ~ 90% pure by HNMR spectroscopy. The solid was purified by slow evaporation by recrystallization from CH ₂ Cl ₂ -hexane (20 mL - 20 mL) to give the pure product as colorless crystals (1.33 g, 43.2% from the ligand). The mother liquor was further concentrated for second harvest (0.291 g, 9.5% from the ligand).

Complex _{(Q3) Zr (NMe 2)} 2. decane (10 mL) for _{Q3-H 2 (0.102 g,} 0.20 mmol) and Zr (NMe ₂₎ was added to _{4 (0.055 g, 0.21 mmol)} . The mixture was heated to 100 < 0 > C overnight. The volatiles were then removed under a stream of nitrogen and the residue was washed with pentane (3 mL). Yield: 0.95 g, 69%.

Complex (Q3) ZrMe _2. was added to toluene (4 mL) to _{(Q3) Zr (NMe 2)} 2 (0.026 g, 0.037 mmol) to form a solution. Trimethylaluminum (0.027 g, 0.38 mmol) in toluene (3 mL) was added and the mixture was stirred for 1 h. The volatiles were removed under a stream of nitrogen. The resulting solid was recrystallized from pentane at -40 < 0 > C. Yield: 6.0 mg, 26%.

Olefin polymerization in a parallel pressure reactor

Catalyst screening for olefin polymerization is described in US 6,306,658, which is incorporated herein by reference in its entirety to the extent that it is not inconsistent with this disclosure; US 6,455,316; US 6,489,168; WO 00/09255; And J. Am. Chem. Soc., 2003, 125, pp. (PPR) as described generally in EP-A-4306-4317. The catalysts are screened in PPR for their ability to produce various polymers including homopolyethylene, homopolypropylene, ethylene-hexene copolymer, ethylene-octene copolymer, and ethylene-propylene copolymer. The following describes the general procedure used to screen the catalyst. The desired temperature, pressure, amount of chemical used (eg, catalyst, activator, scavenger, etc.) can vary from experiment to experiment and specific values are given at the table (or just above or below the table) .

Pre-weighed glass vial inserts and disposable agitated pellets were placed in each reaction vessel of a reactor containing 48 individual reaction vessels. The reactor was purged with a gaseous monomer (typically ethylene or propylene) used for polymerization. If desired, the liquid comonomer (typically 1-octene or 1-hexene) may be injected into each reaction vessel via a valve and then the total reaction volume, including subsequent additions to sufficient solvent (typically isohexane) Volume (typically 5 mL). The reactor was then closed and each vessel was individually heated to the target temperature and pressure and pressurized with gaseous monomers. The contents of the vessel were then stirred at 800 rpm. A solution of scavenger (typically an organoaluminum reagent in isohexane or toluene) was then added with a solvent chaser (typically 500 microliters). An activator solution in toluene (typically 1.1 molar equivalents relative to the precatalyst complex) was introduced into the reaction vessel with a solvent chaser (typically 500 microliters). The toluene solution of the dissolved precatalyst complex was then added with a solvent chaser (typically 500 microliters).

(Typically 6 psi = 0.069 MPa for propylene polymerization performed at 100 psi, typically 12 psi = 0.137 MPa for ethylene-octene copolymerization performed at 75 psi) until a given amount of pressure is absorbed by polymerization ) Or until a defined amount of time has elapsed (typically 30 minutes). At this point, the reaction was quenched by pressurizing the vessel with compressed air or carbon dioxide. After the polymerization reaction, the glass vial insert containing the polymer product and the solvent was removed from the reactor and the inert atmosphere globe box and the volatile components were passed through a Genevac HT-12 centrifuge operating at high temperature and reduced pressure and a Genevac VC3000D vacuum And then removed using an evaporator. The vial was then weighed to determine the yield of polymer product. The resulting polymer was analyzed by Rapid GPC (see below) to determine the molecular weight.

To determine various molecular weight related values by GPC, US 6,491,816; US 6,491,823; US 6,475,391; US 6,461,515; US 6,436,292; US 6,406,632; US 6,175,409; US 6,454,947; US 6,260,407; And high temperature size exclusion chromatography using an automated " Rapid GPC " system as generally described in US 6,294,388. The device has three series of 30 cm x 7.5 mm linear columns each containing PLgel 10 um, Mix B. The GPC system was calibrated using a polystyrene standard ranging from 580 g / mol to 3,390,000 g / mol. The system was operated at an eluent flow rate of 2.0 mL / min and an oven temperature of 165 < 0 > C. 1,2,4-trichlorobenzene was used as an eluent. The polymer samples were dissolved in 1,2,4-trichlorobenzene at a concentration of 0.1 - 0.9 mg / mL. 250 μL of polymer solution was injected into the system. The concentration of polymer in the eluent was monitored using an evaporative light scattering detector. The molecular weights given in the examples are proportional to linear polystyrene standards.

The octene comonomer content in the ethylene-octene copolymer sample was determined by infrared spectroscopy. A sample for infrared analysis was prepared by depositing a stabilized polymer solution on a silanized wafer (part no. S10860, Symyx). By this method, approximately 0.12 to 0.24 mg of polymer is deposited on the wafer cell. Samples were subsequently analyzed on a Brucker Equinox 55 FTIR spectrometer equipped with a Pikes MappIR mirror reflectance sample accessory. Spectra covering the spectral range from 5000 cm ^-1 to 500 cm ^-1 were collected at 2 cm ^-1 resolution in 32 scans. For ethylene-1-octene copolymers, the weight percent comonomer is determined by measuring the methyl modification band at ~ 1375 cm ^-1 . The peak heights of this band are normalized to the combination and overton band at ~ 4321 cm ^-1 , which corrects for the path length difference. The standardized peak height correlates with the individual calibration curve from ¹ H NMR data to predict the com- pound% comonomer in octane concentrations ranging from ~ 2 to 35 wt-%. Typically an R ² correlation of 0.98 or greater is achieved.

Differential Scanning Calorimetry (DSC) measurements were performed on a TA-Q100 instrument to determine the melting point of the polymer. The sample was pre-annealed at 220 < 0 > C for 15 minutes and then cooled to room temperature overnight. The sample was heated to 220 占 폚 at a rate of 100 占 폚 / min and then cooled at a rate of 50 占 폚 / min. The melting point was collected during the heating period.

Ethylene homopolymer

(Q1) HfMe2, (Q2) HfMe2, (Q3) HfMe2 and (Q4) HfMe2 were evaluated as catalyst components for the homopolymerization of ethylene. Table 1 shows data on these executions. The catalytic activity is in the range of 78-100 kg / mmol Hf / h / bar.

[Table 1]

Ethylene- Octen  Copolymerization

(Q1) HfMe2, (Q2) HfMe2, (Q3) HfMe2, and (Q4) HfMe2 were evaluated as catalyst components for copolymerization of ethylene and 1-octene. Table 2 shows data on these executions. Each catalyst was used under the same conditions for multiple runs, and significant scattering in the data is evident in catalytic activity. The catalytic activity is in the range of 45-140 kg / mmol Hf / h / bar. The comonomer incorporation is significant as evidenced by the polyethylene having a lower melting point (87 DEG C-92 DEG C) than the polyethylene homopolymer of Table 1.

[Table 2]

Propylene homopolymerization

(Q1) HfMe2, (Q2) HfMe2, (Q3) HfMe2, and (Q4) HfMe2 were evaluated as catalyst components for the homopolymerization of propylene. Table 3 shows data on these executions. Runs were performed at 70 ° C / 120 psi or 100 ° C / 150 psi. At 70 ℃, the catalytic activity ranged from 167-581 kg / mmol Hf / h, but at 100 ℃ the activity was lower than 10-103 kg / mmol Hf / h. Since complexes prepared with Q3 ligands are highly active at all temperatures, the choice of ligand has a significant effect on the activity of the catalyst. The ligand also has a great influence on the stereoregularity of the produced polypropylene. The complexes prepared using ligands Q2 and Q4 produced polypropylenes with higher melting points than the complexes prepared using ligands Q1 and Q3. The increased polypropylene stereoregularity is believed to be due to the steric bulk of the group at the R ¹³ position (e.g. Ph <ortho-tolyl xylyl) and the dihydro-1H-indenyl J group instead of the phenylmethyl J group (R ¹³ + J refers to formulas I and II).

[Table 3]

Additional complexes (CAT-1, CAT-2, and CAT-3) were synthesized and used for ethylene-propylene copolymerization in a continuous reactor. These were compared with (Q5) HfMe2.

Cat-1 was prepared as described in US 9,102,773. Cat-2 was prepared using the general method described in US 9,315,526. Cat-3 was synthesized according to the procedure described in US 9,290,519.

The following examples were prepared using a solution process in a 1 liter continuous stirred tank reactor (autoclave reactor). The 1 liter autoclave reactor is equipped with a water / steam heating element with stirrer, pressure regulator and thermostat. The reactor was operated under liquid charge conditions at reactor pressure exceeding the bubbling pressure of the reaction mixture while maintaining the reactants in the liquid phase. Isohexane and propylene were pumped to the reactor by a Pulsa feed pump. All flow rates of the liquid were controlled using a Coriolis mass flow controller (Brooks, Quantum series). Ethylene and hydrogen flowed through the Brooks flow regulator into the gas under its own pressure. The monomers (e.g., ethylene and propylene) and hydrogen feed were combined in one stream and then mixed with a precooled isohexane stream cooled to at least 0 &lt; 0 &gt; C. The mixture was then fed into the reactor via a single line. Shortly before entering the reactor, the scavenger solution was also added to the combined solvent and monomer streams to further reduce any catalyst poisons. Similarly, the catalyst solution was fed to the reactor using an ISCO syringe pump over a separate line.

The polymer produced in the reactor was discharged through a back pressure regulating valve which was reduced to atmospheric pressure. This causes the unconverted monomers in the solution to flash from the top of the vapor liquid separator to the evacuated vapor phase. A liquid phase comprising mainly polymer and solvent was collected for polymer recovery. The collected samples were first air-dried in a hood to evaporate most of the solvent and then dried in a vacuum oven at a temperature of about 90 DEG C for about 12 hours. The vacuum oven dried sample was weighed to yield.

The catalysts used in these examples were Cat-1, Cat-2, Cat-3 and (Q5) HfMe2. The activator used was N, N-dimethylanilinium tetrakis (perfluorophenyl) borate (BF2O). Both the catalyst and the activator were first dissolved in toluene and the solution was kept in an inert atmosphere. Premixed solution of the catalyst and activator were fed into the reactor using ISCO syringe pumps ^TM. The feed ratio (moles) of the catalyst to the activator was set to 0.98. A solution of tri-n-octylaluminum (TNOAL) (available from Sigma Aldrich, Milwaukee, Wis.) Was further diluted in isohexane and used as a scavenger.

Runs 1 through 14 are presented as a comparison. Runs 15 to 28 are inventions.

Specific polymerization process conditions and some properties are listed in Table A. The scavenger feed rate was adjusted to optimize catalyst efficiency and the feed rate was varied from 0 (no scavenger) to 15 μmol / min. The catalyst feed rates were adjusted according to the impurity levels in the system to reach the listed target conversion rates. All reactions were carried out at a pressure of about 2.4 MPa / g unless otherwise stated. Additional processing conditions for the polymerization processes of Examples 1 to 28 and the properties of the polymers produced are included in Table A below. The ethylene content was determined by FTIR, ASTM D3900. The melt flow rate (MFR) was determined according to ASTM 1238 (230 占 폚, 2.16 kg) and presented as dg polymer / min.

Runs 15 to 22 demonstrate that the catalyst system (Q5) HfMe2 / BF20 produces a high molecular weight ethylene-propylene copolymer containing 7.0-16.4% of ethylene at 85 ° C with a productivity of 94 kg polymer / mmol Hf or higher. Under similar process conditions, the comparative catalyst has a productivity of 55 kg / mmol Hf or less (see Runs 3 and 5-14).

Runs 25-28 demonstrate that (Q5) HfMe2 / BF20 produces a high molecular weight ethylene-propylene copolymer containing 10-16% ethylene at 100 ° C with a productivity of over 82 kg polymer / mmol Hf. Under similar conditions, CAT-1 / BF20 has a productivity of 19 kg / mmol Hf (see Run 4).

[Table A]

All documents described herein are incorporated by reference herein, including any priority documents and / or test procedures, to the extent that they are not inconsistent with the present disclosure. While forms of the invention have been illustrated and described, as apparent from the foregoing general description and specific embodiments, various modifications may be made without departing from the spirit and scope of the invention. Therefore, the present invention is not intended to be limited thereto. Likewise, the term " comprising " is considered synonymous with the term " including ". Likewise, whenever a constituent, element or group of elements precedes a transitional phrase " comprising ", consisting essentially of " consisting essentially of "quot;, " consisting of ", " selected from the group of consisting of, " or " is ", and vice versa.

Claims (26)

A quinolinyldiamido transition metal complex represented by the following formula (I): &lt; EMI ID =

In the formula,
M is a 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 metal;
J is a triatomic length bridge between quinoline and amido nitrogen;
X is an anionic leaving group;
L is a neutral Lewis base;
R ¹ and R ¹³ is independently selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, and silyl groups;
R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are independently selected from the group consisting of hydrogen, hydrocarbyl, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyl, halogen, and phosphino ;
n is 1 or 2;
m is 0, 1, or 2;
n + m is 4 or less;
Any two adjacent R groups (e.g., R ¹ and R ² , R ² and R ^3, etc.) may be combined to form a substituted hydrocarbyl, unsubstituted hydrocarbyl, substituted heterocyclic ring, A heterocyclic ring, which ring has 5, 6, 7, or 8 ring atoms and the substitutions on the ring may combine to form an additional ring;
Any two X groups may be joined together to form a dianionic group;
Any two L groups may be joined together to form a bidentate Lewis base;
The X group may be bonded to the L group to form a monoanionic two-sided group. The complex of claim 1, wherein J is selected from the following structures:

In the formula,

Represents the connection to the complex. The complex of claim 1, wherein the complex is further represented by formula (II) or (III), preferably (III)

In the formula,
M, L, X, m, n, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ¹³ are as defined in claim 1;
E is carbon, silicon, or germanium;
R ⁷ to R ¹² and R ¹⁴ is independently selected from the group consisting of hydrogen, hydrocarbyl, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyl, halogen;
Any two R groups may be joined to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring having 5, 6, 7, or 8 ring atoms, A ring can be formed. 4. The compound of claim 3 wherein R &lt; ¹¹ &gt; and R ¹² is independently selected from hydrogen, methyl, ethyl, phenyl, isopropyl, isobutyl, and trimethylsilyl. The complex according to claim 3 or 4, wherein E is carbon. 6. A compound according to any one of claims 3, 4 or 5 wherein R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are independently hydrogen, methyl, ethyl, propyl, isopropyl, phenyl, cyclohexyl, Fluoro, chloro, methoxy, ethoxy, phenoxy, and trimethylsilyl.  7. The complex according to any one of claims 1 to 6, wherein M is Ti, Zr or Hf. 8. Compounds according to any one of claims 1 to 7, wherein R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are independently selected from hydrogen, hydrocarbyl, alkoxy, silyl, amino, substituted hydrocarbyl, And halogen. The method according to any one of claims 1 to 8, wherein each L is independently selected from Et ₂ O, MeOtBu, Et ₃ N, PhNMe _2, MePh ₂ N, tetrahydrofuran, and dimethyl selected from sulfide and / or ; Each X is independently selected from the group consisting of methyl, benzyl, trimethylsilyl, neopentyl, ethyl, propyl, butyl, phenyl, hydrido, chloro, fluoro, bromo, iodo, dimethylamido, diethylamido, Amido, and diisopropylamido. &Lt; / RTI &gt; 10. A compound according to any one of claims 1 to 9, wherein R &lt; ^{1 &gt;} is 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2,6- diisopropyl- , 6-diethylphenyl, 2-ethyl-6-isopropylphenyl, 2,6-bis (3-pentyl) phenyl, 2,6-dicyclopentylphenyl or 2,6-dicyclohexylphenyl. The method according to any one of claims 10, wherein, R ¹³ is phenyl, 2-methylphenyl, 2-ethylphenyl, 2-propylphenyl, 2,6-dimethylphenyl, 2-isopropyl-phenyl, 4-methylphenyl, 3-methylphenyl, 4-dimethylaminophenyl, or 2-phenylphenyl. 2. The complex of claim 1 wherein J is dihydro-1H-indenyl and R &lt; ¹ &gt; is 2,6-dialkylphenyl or 2,4,6-trialkylphenyl. 13. Compounds according to any one of claims 1 to 12, wherein R &lt; ¹ &gt; is 2,6-diisopropylphenyl and R &lt; ¹³ &gt; is selected from the group consisting of 1,2, 3,4, 5,6 or 7 carbon atoms Complexes with hydrocarbyl groups. 14. Compounds according to any of claims 3 to 13, wherein R &lt; ¹⁰ &gt; and R &lt; ¹¹ &gt; is bonded to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring, said ring having 5, 6, 7, or 8 ring atoms (preferably 6 atoms) Are able to combine to form additional rings. The method of claim 3,
R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are independently selected from the group consisting of hydrogen, hydrocarbyl, alkoxy, silyl, amino, substituted hydrocarbyl, and halogen;
R ¹ is selected from the group consisting of 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2,6-diisopropyl-4-methylphenyl, 2,6- Propylphenyl, 2,6-bis (3-pentyl) phenyl, 2,6-dicyclopentylphenyl, or 2,6-dicyclohexylphenyl;
R ¹³ is selected from the group consisting of phenyl, 2- methylphenyl, 2-ethylphenyl, 2-propylphenyl, 2,6-dimethylphenyl, -Butylphenyl, 4-fluorophenyl, 3-methylphenyl, 4-dimethylaminophenyl, or 2-phenylphenyl;
R &lt; ¹¹ & R ¹² is independently selected from hydrogen, methyl, ethyl, phenyl, isopropyl, isobutyl, and trimethylsilyl;
E is carbon;
R ^7, R ^8, R ^9, and R ¹⁰ are independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, phenyl, cyclohexyl, fluoro, chloro, methoxy, ethoxy, phenoxy, trimethylsilyl Being;
And M is Ti, Zr, or Hf. The method according to claim 1,
R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are independently selected from the group consisting of hydrogen, hydrocarbyl, alkoxy, silyl, amino, substituted hydrocarbyl, and halogen;
R ¹ is selected from the group consisting of 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2,6-diisopropyl-4-methylphenyl, 2,6- Propylphenyl, 2,6-bis (3-pentyl) phenyl, 2,6-dicyclopentylphenyl, or 2,6-dicyclohexylphenyl; R ¹³ is selected from the group consisting of phenyl, 2- methylphenyl, 2-ethylphenyl, 2-propylphenyl, 2,6-dimethylphenyl, -Butylphenyl, 4-fluorophenyl, 3-methylphenyl, 4-dimethylaminophenyl, or 2-phenylphenyl;
R ¹³ is selected from the group consisting of phenyl, 2- methylphenyl, 2-ethylphenyl, 2-propylphenyl, 2,6-dimethylphenyl, -Butylphenyl, 4-fluorophenyl, 3-methylphenyl, 4-dimethylaminophenyl, or 2-phenylphenyl;
J is selected from the following structures,

In the formula,

Lt; / RTI &gt; represents the connection to the complex;
M is Ti, Zr, or Hf. A quinolinyldiamido transition metal complex represented by the following formula:

A catalyst system comprising an activator and a transition metal complex of any one of claims 1 to 17. 19. The catalyst system of claim 18, wherein at least two catalyst complexes are present. The catalyst system according to claim 18 or 19, wherein the activator is an alumoxane and / or a non-coordinating anion. 21. A catalyst system according to any one of claims 18, 19 or 20, wherein the catalyst complex and / or the activator are supported. Contacting the at least one olefin monomer with the catalyst system of any one of claims 18 to 21 and obtaining the olefin polymer, preferably ethylene and / or propylene, preferably a polymerization process for producing polyolefins, Lt; / RTI &gt; Contacting at least one olefin monomer with a catalyst system comprising the complex and the activator of any of claims 18 to 21 at a temperature of at least 85 캜 in a solution phase and obtaining an olefin polymer, And wherein the olefin monomer comprises ethylene and propylene. 24. The polymerization process according to claim 22 or 23, wherein the polyolefin produced is an ethylene polymer or a propylene polymer, preferably isotactic polypropylene. Contacting the at least one olefin monomer with a catalyst system comprising the complex of claim 25 and a activator at a temperature of at least 85 &lt; 0 &gt; C, and obtaining an olefin polymer, wherein the olefin monomer comprises ethylene and propylene Wherein the olefin polymer has a melt flow rate (230 占 폚, 2.16 kg) of less than 1.0 dg / min. 26. The method of claim 25, wherein the activator is a non-coordinating anion.

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