Pyridyldiamido transition metal complexes, their production and use

文档序号：965409 发布日期：2020-11-03 浏览：16次中文

阅读说明：本技术 吡啶基二氨基过渡金属络合物，其的生产和用途 (Pyridyldiamido transition metal complexes, their production and use ) 是由 J·R·哈格多恩 I·S·波里索夫 A·K·格里尼施契夫 G·P·戈于诺夫 D·V·乌博斯基于 2014-11-13 设计创作，主要内容包括：公开了将吡啶基二氨基过渡金属络合物与任选的链转移剂一起用于烯烃聚合中。(Pyridyldiamido transition metal complexes are disclosed for use in olefin polymerization, along with optional chain transfer agents.)

1. A process of the formula: (A) a pyridyldiamido transition metal complex represented by (A), (B), (C) or (D):

wherein:

m is Ti, Zr or Hf;

Q¹is a triatomic bridge of the formula and centered on the triatomic bridge is a group 15 or 16 element (said group 15 element may or may not be R)³⁰Substituted with groups): -G¹-G²-G³-, where G is²Is a group 15 or 16 atom (said group 15 element may be represented by R)³⁰Substituted with radicals), G¹And G³Each being a group 14, 15 or 16 atom (each group 14, 15 and 16 element may or may not be one or more R's)³⁰Substituted by radicals) G here¹、G²And G³Or G¹And G²Or G¹And G³Or G²And G³Mono-or polycyclic ring systems can be formed;

each R³⁰The radicals being independently hydrogen or C₁-C₁₀₀A hydrocarbyl or silyl group;

Q²is-NR¹⁷、-PR¹⁷Or oxygen, where R¹⁷Selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, silyl, and germyl;

Q³is- (TT) -or- (TTT) -, where each T is a carbon or heteroatom, and said carbon or heteroatom may be unsubstituted or substituted with one or more R³⁰Substituted by radicals, with "-C-Q³Together, the ═ C- "segments form a 5-or 6-membered cyclic group or a polycyclic group comprising a 5-or 6-membered cyclic group;

R¹selected from hydrocarbyl, and substituted hydrocarbyl, or silyl;

R³、R⁴and R⁵Independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, alkoxy, aryloxy, halogen, amino and silyl, and wherein adjacent R groups (R)³And R⁴And/or R⁴And R⁵) May combine to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5,6, 7 or 8 ring atoms, and where substituents on the ring may combine to form additional rings;

R²is-E (R)¹²)(R¹³) -, and E is carbon, silicon or germanium;

y is selected from oxygen, sulfur and-E (R)⁶)(R⁷) And E is carbon, silicon or germanium;

R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²and R¹³Independently selected from hydrogen, hydrocarbyl, substitutedHydrocarbyl, alkoxy, halogen, amino and silyl groups, and wherein adjacent R groups (R)⁶And R⁷And/or R⁸And R⁹And/or R⁹And R¹⁰And/or R¹⁰And R¹¹And/or R¹²And R¹³) May combine to form a saturated, substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5,6, 7 or 8 ring carbon atoms, and where substituents on the ring may combine to form additional rings;

l is an anionic leaving group, where the L groups may be the same or different, and any two L groups may be linked to form a dianionic leaving group;

n is 0, 1,2,3 or 4;

l' is a neutral lewis base; and

w is 0, 1,2,3 or 4.

2. The complex of claim 1, wherein R²Is selected from CH₂CH (aryl), CH (2-isopropylphenyl), CH (2, 6-dimethylphenyl), CH (2, 4-6-trimethylphenyl), CH (alkyl), CMe₂、SiMe₂、SiEt₂And SiPh₂。

3. The complex of claim 1, wherein E and E are carbon and each R⁶、R⁷、R¹²And R¹³Is C₁-C₃₀Substituted or unsubstituted hydrocarbyl.

4. The complex of claim 1, wherein E and E are carbon and R¹And R¹⁷Independently selected from phenyl, substituted with 0, 1,2,3,4 or 5 substituents selected from: F. cl, Br, I, CF₃、NO₂Alkoxy, dialkylamino, hydrocarbyl and substituted hydrocarbyl having 1-10 carbons.

5. The complex of claim 1, wherein Q¹Selected from:

here, the

6. The complex of claim 1, wherein each L is independently selected from the group consisting of halide, alkyl, aryl, alkoxy, amino, hydride, phenoxy, hydroxy, silyl, allyl, alkenyl, trifluoromethanesulfonate, alkylsulfonate, arylsulfonate, and alkynyl; and each L' is independently selected from the group consisting of ethers, thioethers, amines, nitriles, imines, pyridines, and phosphines.

7. A catalyst system comprising an activator and the complex of claim 1.

8. A polymerization process comprising contacting one or more olefin monomers with a catalyst system comprising: i) an activator, and ii) the pyridyldiamido transition metal complex of claim 1.

9. A composition comprising the catalyst system of claim 7 and a chain transfer agent.

Technical Field

The present invention relates to pyridyldiamido transition metal complexes and intermediates and processes for making such pyridyldiamido complexes. The transition metal complexes can be used as catalysts in olefin polymerization processes.

Background

Pyridylamines have been used to prepare group 4 complexes, which are useful transition metal components for olefin polymerization, see, e.g., US 2002/0142912; US 6900321; and US6103657, where the ligands have been used in complexes in which the ligands are bidentate to the transition metal atom.

WO2005/095469 shows catalyst compounds which use tridentate ligands via two nitrogen atoms (one amide and one pyridyl group) and one oxygen atom.

US2004/0220050a1 and WO2007/067965 disclose complexes in which the ligand is coordinated in a tridentate manner by two nitrogens (one amide and one pyridyl group) and one carbon (aryl anion) donor.

One key step in the activation of these complexes is the insertion of olefins into the metal-aryl bond of the catalyst precursor (Froese, r.d.j. et al, j.am.chem.soc.2007, 129, page 7831-7840) to form an active catalyst having five-and seven-membered chelate rings.

WO2010/037059 discloses pyridine-containing amines for use in medical applications.

US2010/0227990a1 discloses ligands that are bound to a metal center with a group of NNC donors, instead of the NNN or NNP donor groups.

WO/0238628A2 discloses ligands which are bound to the metal center with a group of NNC donors instead of a group of NNN or NNP donors.

Guerin, f.; McConville, d.h.; vital, j.j. organometallics 1996, 15, page 5586 discloses a ligand group and group 4 complex that uses the NNN donor group but does not have the characteristic 7-membered chelate ring or indanyl and tetralinyl.

US7973116, US8394902, US2011-0224391, US2011-0301310a1 and USSN61/815065 (filed 4/23.2013) disclose pyridylamide transition metal complexes which are free of the characteristic indanyl or tetrahydronaphthyl groups.

Also contemplated are references including 1) Vaughan, a; davis, d.s.; hagadorn, J.R., Comprehensive Polymer Science, Vol.3, Chapter 20, "Industrial Catalysts for engineering polymerization"; 2) gibson, v.c.; spitzmesser, s.k.chem.rev.2003, 103, 283; and 3) Britovsek, G.J.P.; gibson, v.c.; wass, d.f.angelw.chem.int.ed.1999, 38, 428.

There remains a need to increase the synthetic routes to broaden the scope of catalyst complexes which can make and broaden their performance in olefin polymerization. This property may vary in the following respects: the amount of polymer produced per unit amount of catalyst under the prevailing polymerization conditions (commonly referred to as "activity"); the molecular weight and molecular weight distribution achieved at a given temperature; and/or a higher alpha-olefin arrangement in terms of stereoregular arrangement. In particular, improvement of catalyst activity is of industrial interest because it directly affects economic feasibility.

Disclosure of Invention

The present invention relates to novel transition metal complexes having tridentate ligands, such as tridentate NNN or NNP ligands. The ligand may be derived from a neutral ligand precursor or may be generated in situ in the complex. The invention also relates to pyridyldiamido transition metal complexes of the general formula (A), (B), (C) or (D) and to catalyst systems comprising an activator and a pyridyldiamido transition metal complex of the formula (A), (B), (C) or (D):

wherein:

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

Q¹is a triatomic bridge and the triatomic center is a group 15 or 16 element (said group 15 element may or may not be R)³⁰Substituted with groups) which preferably form a coordinate bond to M, preferably with the formula: -G¹-G²-G³-represents, here G²Is a group 15 or 16 atom (said group 15 element may be represented by R)³⁰Substituted with radicals), G¹And G³Each being a group 14, 15 or 16 atom (each group 14, 15 and 16 element may or may not be one or more R's)³⁰Substituted by radicals) G here¹、G²And G³Or G¹And G²Or G¹And G³Or G²And G³May form a mono-or polycyclic ring system, where each R is³⁰The radicals being independently hydrogen or C₁-C₁₀₀A hydrocarbyl or silyl group;

Q²is-NR¹⁷、-PR¹⁷Or oxygen, where R¹⁷Selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, silyl, and germyl;

Q³is- (TT) -or- (TTT) -, where each T is a carbon or heteroatom, preferably C, O, S or N, and said carbon or heteroatom may be unsubstituted (e.g. hydrogen bonded to the carbon or heteroatomOn carbon or hetero atoms) or with one or more R³⁰Substituted by radicals, with "-C-Q³Together, the ═ C- "segments form a 5-or 6-membered cyclic group or a polycyclic group comprising a 5-or 6-membered cyclic group;

R¹selected from hydrocarbyl, and substituted hydrocarbyl, or silyl;

R²is-E (R)¹²)(R¹³) -, and E is carbon, silicon or germanium;

y is selected from oxygen, sulfur and-E (R)⁶)(R⁷) And E is carbon, silicon or germanium;

R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²and R¹³Independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, alkoxy, halo, amino and silyl, and wherein adjacent R groups (R)⁶And R⁷And/or R⁸And R⁹And/or R⁹And R¹⁰And/or R¹⁰And R¹¹And/or R¹²And R¹³) May combine to form a saturated, substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5,6, 7 or 8 ring carbon atoms, and where substituents on the ring may combine to form additional rings;

l is an anionic leaving group, where the L groups may be the same or different, and any two L groups may be linked to form a dianionic leaving group;

n is 0, 1,2,3 or 4;

l' is a neutral lewis base; and

w is 0, 1,2,3 or 4.

The invention further relates to a process for making the above complex, a process for making an intermediate for the above complex and a process for polymerizing olefins using the above complex.

The invention further relates to a process for the polymerization of olefins using the above complexes in the presence of a chain transfer agent.

The present application also relates to the following embodiments:

1. a process of the formula: (A) a pyridyldiamido transition metal complex represented by (A), (B), (C) or (D):

wherein:

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

each R³⁰The radicals being independently hydrogen or C₁-C₁₀₀A hydrocarbyl or silyl group;

Q²is-NR¹⁷、-PR¹⁷Or oxygen, where R¹⁷Selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, silyl, and germyl;

Q³is- (TT) -or- (TTT) -, where each T is a carbon or heteroatom, andthe carbon or hetero atoms may be unsubstituted or substituted with one or more R³⁰Substituted by radicals, with "-C-Q³Together, the ═ C- "segments form a 5-or 6-membered cyclic group or a polycyclic group comprising a 5-or 6-membered cyclic group;

R¹selected from hydrocarbyl, and substituted hydrocarbyl, or silyl;

R²is-E (R)¹²)(R¹³) -, and E is carbon, silicon or germanium;

y is selected from oxygen, sulfur and-E (R)⁶)(R⁷) And E is carbon, silicon or germanium;

l is an anionic leaving group, where the L groups may be the same or different, and any two L groups may be linked to form a dianionic leaving group;

n is 0, 1,2,3 or 4;

l' is a neutral lewis base; and

w is 0, 1,2,3 or 4.

2. The complex of embodiment 1, wherein M is Ti, Zr, or Hf.

3. The complex of embodiment 1 wherein R²Is selected from CH₂CH (aryl), CH (2-isopropylphenyl), CH (2, 6-dimethylphenyl), CH (2, 4-6-trimethylphenyl), CH (alkyl), CMe₂、SiMe₂、SiEt₂And SiPh₂。

4. The complex of embodiment 1 wherein T is C, O, S or N.

5. The complex of embodiment 1, wherein E and E are carbon and each R⁶、R⁷、R¹²And R¹³Is C₁-C₃₀Substituted or unsubstituted hydrocarbyl.

6. The complex of embodiment 1, wherein E and E are carbon and each R⁶、R⁷、R¹²And R¹³Is C₆-C₃₀Substituted or unsubstituted aryl.

7. The complex of embodiment 1 wherein Q²is-NR¹⁷。

8. The complex of embodiment 1, wherein E and E are carbon and R¹And R¹⁷Independently selected from phenyl, substituted with 0, 1,2,3,4 or 5 substituents selected from: F. cl, Br, I, CF₃、NO₂Alkoxy, dialkylamino, hydrocarbyl and substituted hydrocarbyl having 1-10 carbons.

9. The complex of embodiment 1 wherein Q¹Selected from:

here, the

The symbolic representation is connected to R²And an aromatic ring, and alkyl is an alkyl group.

10. The complex of embodiment 1, wherein each L is independently selected from the group consisting of halide, alkyl, aryl, alkoxy, amino, hydride, phenoxy, hydroxy, silyl, allyl, alkenyl, trifluoromethanesulfonate, alkylsulfonate, arylsulfonate, and alkynyl; and each L' is independently selected from the group consisting of ethers, thioethers, amines, nitriles, imines, pyridines, and phosphines.

11. The complex of embodiment 1 wherein Q³Is CHCHCHCH, CHCH, CHN (alkyl), CH-S, CHC (alkyl) CH, C (alkyl) CHC (alkyl), CH-O or NO.

12. The complex of embodiment 1, wherein the complex is represented by formula (a).

13. The complex of embodiment 1, wherein the complex is represented by formula (B).

14. The complex of embodiment 1, wherein the complex is represented by formula (C).

15. The complex of embodiment 1, wherein the complex is represented by formula (D).

16. A catalyst system comprising an activator and the complex of embodiment 1.

17. The catalyst system of embodiment 16 wherein the activator comprises an alumoxane.

18. The catalyst system of embodiment 16, wherein the activator comprises a non-coordinating anion.

19. The catalyst system of embodiment 16, wherein the activator comprises one or more of:

trimethylammonium tetrakis (perfluoronaphthyl) borate, N, N-dimethylanilinium tetrakis (perfluoronaphthyl) borate, N, N-diethylanilinium tetrakis (perfluoronaphthyl) borate, triphenylcarbenium tetrakis (perfluoronaphthyl) borate, trimethylammonium tetrakis (perfluorobiphenyl) borate, N, N-dimethylanilinium tetrakis (perfluorobiphenyl) borate, triphenylcarbenium tetrakis (perfluorobiphenyl) borate, 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 (perfluorophenyl) borate, [ Ph.₃C⁺][B(C₆F₅)₄ ^-]，[Me₃NH⁺][B(C₆F₅)₄ ^-]1- (4- (tris (pentafluorophenyl) borate) -2,3,5, 6-tetrafluorophenyl) pyridium, tetrakis (pentafluorophenyl) borate, 4- (tris (pentafluorophenyl) borate) -2,3,5, 6-tetrafluoropyridine, triphenylcarbenium tetraphenylborate, and triphenylcarbenium tetrakis- (2,3,4, 6-tetrafluorophenyl) borate.

20. A polymerization process comprising contacting one or more olefin monomers with a catalyst system comprising: i) an activator, and ii) a pyridyldiamido transition metal complex of embodiment 1.

21. The process of embodiment 20 wherein the activator comprises an alumoxane.

22. The process of embodiment 20 wherein the activator comprises a non-coordinating anion.

23. The method of embodiment 20 wherein the monomer comprises ethylene.

24. The process of embodiment 20 wherein the monomer comprises propylene.

25. The method of embodiment 20, wherein the pyridyldiamido transition metal complex is supported.

26. The method of embodiment 25 wherein the support is silica.

27. The method of embodiment 20 wherein the activator comprises one or more of:

28. The process of embodiment 20 wherein a chain transfer agent is present.

29. The method of embodiment 20 wherein the chain transfer agent is selected from group 2, 12 or 13 alkyl or aryl compounds.

30. The process of embodiment 20 wherein the chain transfer agent is selected from dialkyl zinc compounds where the alkyl groups are independently selected from methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, cyclohexyl, and phenyl.

31. The process of embodiment 20 wherein the presence of the chain transfer agent increases the activity of the catalyst component by at least a factor of 2 relative to the activity under the same conditions in the absence of the chain transfer agent.

32. The process of embodiment 28 wherein the chain transfer agent comprises a dialkylzinc and/or a trialkylaluminum.

33. A composition comprising the catalyst system of embodiment 16 and a chain transfer agent.

Drawings

FIG. 1 is the molecular structure of complex 1, as determined by single crystal X-ray diffraction.

Detailed Description

Transition metal complexes are described herein. The term complex is used to describe a molecule in which an ancillary ligand is coordinated to the central transition metal atom. The ligand is bulky and is stably bonded to the transition metal to maintain its effect during catalyst use, e.g., in polymerization. The ligand may be coordinated to the transition metal by covalent and/or electron donating coordination or intermediate bonding. The transition metal complexes are typically subjected to activation to exert their polymeric or oligomeric function using an activator which is believed to generate cations as a result of the removal of anionic groups (often referred to as leaving groups) from the transition metal.

As used herein, the numbering scheme for the groups of the periodic Table is the new nomenclature set forth in Chemical and Engineering News, 63(5), 27 (1985).

The following abbreviations may be used in the specification: dme is 1, 2-dimethoxyethane, Me is methyl, Ph is phenyl, Et is ethyl, Pr is propyl, iPr is isopropyl, n-Pr is n-propyl, Bu is butyl, iBu is isobutyl, tBu refers to tert-butyl, p-tBu is p-tert-butyl, nBu is n-butyl, TMS is trimethylsilyl, TIBAL is triisobutylaluminum, TNOAL is tri (n-octyl) aluminum, MAO is methylaluminoxane, p-Me is p-methyl, Bn is benzyl (i.e., CH2Ph), THF (also known as THF) is tetrahydrofuran, RT is room temperature (and is 23 ℃, unless otherwise indicated), tol is toluene, EtOAc is ethyl acetate, and Cy is cyclohexyl.

The term "substituted" means that the hydrogen has been replaced with a heteroatom or a hydrocarbyl group. For example, methylcyclopentadiene is substituted with a methyl group.

The terms "hydrocarbyl group," "hydrocarbyl group," and "hydrocarbyl group" are used interchangeably herein. Likewise, the terms "group," "group," and "substituent" are used interchangeably herein. In the present invention, "hydrocarbyl" is defined as C₁-C₁₀₀A group, which may be linear, branched or cyclic, and when cyclic, aromatic or non-aromatic.

Substituted hydrocarbyl is a radical in which at least one hydrogen atom of the hydrocarbyl has been substituted with at least one functional group such as NR x2, OR, SeR, TeR, PR x2, AsR x2, SbR x2, SR, BR x2, SiR x3, GeR x3, SnR x3, PbR x3, etc., OR where at least one heteroatom has been inserted into the hydrocarbyl ring.

The term "catalyst system" is defined to mean a complex/activator pair. When "catalyst system" is used to describe such a pair prior to activation, it means that the unactivated catalyst complex (precatalyst) is together with the activator and optional co-activator. When it is used to describe such a pair after activation, it means the activated complex and an activator or other charge-balancing moiety. The transition metal compound may be neutral, as in the precatalyst, or the charged species may have a counter ion, as in the activated catalyst system.

As used herein, a complex is often also referred to as a catalyst precursor, a precatalyst, a catalyst compound, a transition metal compound or a transition metal complex. These terms are used interchangeably. Activators and cocatalysts are also used interchangeably.

Scavengers are compounds that are typically added to promote polymerization by scavenging impurities. Some scavengers may also act as activators and may be referred to as co-activators. Co-activators (which are not scavengers) may also be used with the activator to form an activated catalyst. In some embodiments, the co-activator may be premixed with the transition metal compound to form an alkylated transition metal compound.

A non-coordinating anion (NCA) is defined to mean an anion that does not coordinate to the catalyst metal cation or that coordinates to the metal cation, but is only weakly coordinated. The term NCA is also defined to include multi-component NCA-containing activators such as N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate that contains an acidic cationic group and a non-coordinating anion. The term NCA is also defined to include neutral lewis acids, such as tris (pentafluorophenyl) boron, which can react with a catalyst to form an activated species by abstraction of an anionic group. NCA coordinates weakly enough that neutral lewis bases such as ethylenically unsaturated monomers can displace it from the catalyst center. Any metal or metalloid that can form a compatible, weakly coordinating complex or be contained in a noncoordinating anion can be used. Suitable metals include, but are not limited to, aluminum, gold, and platinum. Suitable non-metals include, but are not limited to, boron, aluminum, phosphorus, and silicon. The stoichiometric ratio of activator can be neutral or ionic. The terms ionic activator and stoichiometric ionic activator may be used interchangeably. Likewise, the terms neutral stoichiometric activator and lewis acid activator may be used interchangeably. The term non-coordinating anion includes neutral stoichiometric activators, ionic activators and lewis acid activators.

An "olefin" is alternatively referred to herein as an "alkene," which is a linear, branched, or cyclic compound comprising carbon and hydrogen, having at least one double bond. In this specification and in the claims thereto, when a polymer or copolymer is referred to as comprising an olefin, the olefin present in such polymer or copolymer is an olefin in polymerized form. For example, when a copolymer is referred to as having a "propylene" content of 35 wt% to 55 wt%, it is understood that the monomer units of the copolymer are derived from propylene in the polymerization reaction, and the derived units are present in an amount of 35 wt% to 55 wt% based on the weight of the copolymer.

A "polymer" herein has two or more "monomeric" units, which may be the same or different. A "homopolymer" is a polymer of identical monomer units. A "copolymer" is a polymer having two or more monomer units that are different from each other. A "terpolymer" is a polymer having three monomer units that differ from each other. "different" in reference to monomeric units means that the monomeric units differ from each other by at least one atom or are different isomers. Thus, as used herein, the definition of copolymer includes terpolymers and the like. Oligomers are generally polymers having low molecular weights, e.g., Mn less than 25000g/mol, or in one embodiment less than 2500g/mol, or a low number of monomeric units, e.g., 75 monomeric units or less or 50 monomeric units or less. An "ethylene polymer" or "ethylene copolymer" is a polymer or copolymer comprising at least 50 mol% of ethylene derived units, a "propylene polymer" or "propylene copolymer" is a polymer or copolymer comprising at least 50 mol% of propylene derived units, and the like.

Higher alpha-olefins are defined as alpha-olefins having 4 or more carbon atoms.

Unless otherwise specified, all molecular weight units (e.g., Mw, Mn, Mz) are g/mol.

Unless otherwise specified, the total melting point (Tm) is the DSC second melt.

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

The term "aryl" denotes a 6 carbon aromatic ring and substituted variants thereof, including but not limited to phenyl, 2-methylphenyl, xylyl, 4-bromo-xylyl. Likewise heteroaryl denotes an aryl group in which a ring carbon atom (or two or three ring carbon atoms) has been replaced by a heteroatom, preferably N, O or S.

"Ring atom" means an atom which is part of a ring-forming structure. By this definition, benzyl has 6 ring atoms and tetrahydrofuran has 5 ring atoms.

A heterocyclic ring is a ring having a heteroatom in the ring structure, as opposed to a ring in which a hydrogen on a ring atom is replaced with a heteroatom substituted. For example tetrahydrofuran is a heterocyclic ring and 4-N, N-dimethylamino-phenyl is a heteroatom-substituted ring.

As used herein, the term "aromatic" also refers to pseudo-aromatic heterocycles, which are heterocyclic substituents that have similar properties and structures (close to planar) as aromatic heterocyclic ligands, but are not aromatic by definition; also the term aromatic refers to substituted aromatic.

The term "continuous" refers to a system that operates without interruption or stoppage. For example, a continuous process for producing a polymer would be one where reactants are continuously introduced into one or more reactors and polymer product is continuously withdrawn.

Solution polymerization means a polymerization process in which the polymer is dissolved in a liquid polymerization medium such as an inert solvent or monomer or a mixture thereof. Solution polymerization is generally homogeneous. Homogeneous polymerization is polymerization where the polymer product is dissolved in the polymerization medium. Such systems are preferably not turbid as described in j.vladimir oliverira, c.dariva and j.c.pinto, ind.eng, chem.res.29, 2000, 4627.

Bulk polymerization refers to a polymerization process in which the monomer and/or comonomer to be polymerized is used as a solvent or diluent, with little or no inert solvent being used as a solvent or diluent. A small fraction of inert solvent can be used as a carrier for the catalyst and scavenger. The bulk polymerization system comprises less than 25 wt% of inert solvent or diluent, preferably less than 10 wt%, preferably less than 1 wt%, preferably 0 wt%.

In a first aspect of the invention, there is provided a pyridyldiamido transition metal complex (optionally for olefin polymerization) which is prepared by the general formula: (A) (B), (C) or (D), and in another aspect, provided is a catalyst system comprising an activator and one or more pyridyldiamido transition metal complexes of formula (A), (B), (C) or (D) (optionally, for olefin polymerization):

wherein:

m is a group 3,4, 5,6, 7, 8, 9, 10, 11 or 12 metal (preferably a group 4 metal, preferably Ti, Zr or Hf);

Q²is-NR¹⁷、-PR¹⁷Or oxygen, where R¹⁷Selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, silyl, and germyl;

Q³is- (TT) -or- (TTT) -, where each T is a carbon or heteroatom (preferably C, O, S or N), and the carbon or heteroatom may or may not be one or more R³⁰Substituted by radicals, with "-C-Q³Together, the ═ C- "segments form a 5-or 6-membered cyclic group or a polycyclic group comprising a 5-or 6-membered cyclic group;

R¹selected from hydrocarbyl, and substituted hydrocarbyl, or silyl;

R²is-E (R)¹²)(R¹³) -, and E is carbon, silicon or germanium (preferably carbon or silicon, preferably carbon), and the above-mentioned R¹²And R¹³；

Y is selected from oxygen, sulfur and-E (R)⁶)(R⁷) And E is carbon, silicon or germanium (preferably carbon or silicon, preferably carbon) and R as defined herein⁶And R⁷；

L is an anionic leaving group, where the L groups may be the same or different, and any two L groups may be linked to form a dianionic leaving group;

n is 0, 1,2,3 or 4 (preferably 2);

l' is a neutral lewis base; and

w is 0, 1,2,3 or 4 (preferably 0 or 1).

In a preferred embodiment of the invention, Q¹Is one of the following:

this is achieved byThe symbolic representation is connected to R²And aromatic rings, and alkyl is alkyl, e.g. C₁-C₂₀Alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl.

In a preferred embodiment of the invention, G¹Is carbon, nitrogen, oxygen, silicon or sulfur, preferably carbon.

In a preferred embodiment of the invention, G²Is nitrogen, phosphorus, oxygen, sulfur or selenium, preferably nitrogen, oxygen or sulfur.

In a preferred embodiment of the invention, G³Is carbon, nitrogen, oxygen, silicon or sulfur, preferably carbon.

In a preferred embodiment of the invention, Q²Is NR¹⁷，PR¹⁷Or oxygen, preferably NR¹⁷。

In a preferred embodiment of the invention, Q³Is CHCHCHCH, CHCH, CHN (alkyl), CH-S, CHC (alkyl) CH, C (alkyl) CHC (alkyl), CH-O, NO, preferably CHCHCHCH, CHCH, CHN (alkyl), CHN (Me), CH-S, preferably CHCH, CHN (alkyl), CH-SThe alkyl group being C₁-C₂₀Alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl.

In a preferred embodiment of the invention, R¹Selected from hydrocarbyl, substituted hydrocarbyl and silyl groups (preferably alkyl, aryl, heteroaryl, and silyl groups, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, phenyl, substituted phenyl, 2, 6-disubstituted phenyl, 2, 6-diisopropylphenyl, 2, 4-6-trisubstituted aryl, 2,4, 6-triisopropylphenyl and isomers thereof, including cyclohexyl).

In a preferred embodiment of the invention, R¹⁷Selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, silyl, and germyl (preferably alkyl, aryl, heteroaryl, and silyl, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, cycloalkyl, cyclooctyl, cyclododecyl, phenyl, substituted phenyl, 2-substituted phenyl, o-tolyl, 2, 6-disubstituted phenyl and isomers thereof, including cyclohexyl).

In a preferred embodiment of the invention, R³⁰Selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, and silyl (preferably alkyl, aryl, heteroaryl, and silyl, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, phenyl, substituted phenyl and isomers thereof, including cyclohexyl).

In a preferred embodiment of the invention, R²Containing 1-20 carbons, preferably R²Is selected from CH₂CH (aryl), CH (2-isopropylphenyl), CH (2, 6-dimethylphenyl), CH (2, 4-6-trimethylphenyl), CH (alkyl), CMe₂，SiMe₂，SiEt₂And SiPh₂。

In a preferred embodiment of the invention, E and E are independently carbon, silicon or germanium (preferably carbon or silicon, preferably carbon). In a preferred embodiment of the invention, E and E are both carbon.

In a preferred embodiment of the invention, each R is¹²，R¹³，R⁶And R⁷Independently selected from the group consisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl, alkoxy, silyl, amino, aryloxy, halogen, and phosphino (preferably hydrogen, alkyl, aryl, alkoxy, silyl, amino, aryloxy, heteroaryl, halogen, and phosphino), R¹²And R¹³And/or R⁶And R⁷May combine to form a saturated, substituted or unsubstituted hydrocarbyl ring, where the ring has 4,5, 6 or 7 ring carbon atoms and where substituents on the ring may combine to form another ring, or R¹²And R¹³And/or R⁶And R⁷May combine to form a saturated heterocyclic ring, or a saturated substituted heterocyclic ring, where substituents on the ring may combine to form additional rings.

In a preferred embodiment of the invention, R¹²And R¹³At least one is C₁-C₁₀₀(preferably C)₆-C₄₀Preferably C₇-C₃₀Preferably C₈-C₂₀) Substituted or unsubstituted hydrocarbon radicals (preferably aryl, phenyl, substituted phenyl, alkyl-or aryl-substituted phenyl, C₂-C₃₀Alkyl or aryl substituted phenyl, 2-isopropylphenyl, 2,4, 6-trimethylphenyl, etc.).

In a preferred embodiment of the invention, R⁶And R⁷At least one is C₁-C₁₀₀(preferably C)₆-C₄₀Preferably C₇-C₃₀Preferably C₈-C₂₀) Substituted or unsubstituted hydrocarbon radicals (preferably aryl, phenyl, substituted phenyl, alkyl-or aryl-substituted phenyl, C₂-C₃₀Alkyl or aryl substituted phenyl, 2-isopropylphenyl, 2,4, 6-trimethylphenyl, etc.).

In a preferred embodiment of the invention, R³，R⁴And R⁵Independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, alkoxy, aryloxy, halogen, amino and silyl, (preferably hydrogen, alkyl, alkoxy, aryloxy, halogen, amino, silyl and aryl), and wherein adjacent R groups (R³And R⁴And/or R⁴And R⁵) May combine to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5,6, 7 or 8 ring atoms and where substituents on the ring may combine to form a further ring, preferably R³，R⁴And R⁵Independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, phenyl, substituted phenyl and isomers thereof.

In a preferred embodiment of the invention, R⁸，R⁹，R¹⁰And R¹¹Independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, alkoxy, halo, amino and silyl, and in geminal position, and wherein adjacent R groups (R)⁸And R⁹And/or R⁹And R¹⁰And/or R¹⁰And R¹¹) Can combine to form a saturated, substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5,6, 7 or 8 ring carbon atoms and where substituents on the ring can combine to form another ring, preferably R⁸，R⁹，R¹⁰And R¹¹Independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, phenyl, substituted phenyl and isomers thereof.

Preferably the above mentioned R groups and the other R groups mentioned below contain up to 30 carbon atoms, preferably not more than 30 carbon atoms, especially 2 to 20 carbon atoms.

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

In a preferred embodiment of the invention, R1 and R17 can be independently selected from phenyl, which is variously substituted with 0-5 substituents including F, Cl, Br,I，CF₃，NO₂alkoxy, dialkylamino, aryl and alkyl (having 1-10 carbons).

In a preferred embodiment of the invention, each L may be independently selected from the group consisting of halide, alkyl, aryl, alkoxy, amide, hydride, phenoxy, hydroxy, silyl, allyl, alkenyl, trifluoromethanesulfonate, alkylsulfonate, arylsulfonate and alkynyl. The choice of the leaving group depends on the synthetic route used to obtain the complex and can be varied by further reactions to suit the subsequent activation method in the polymerization. Alkyl groups are preferred, for example, when a non-coordinating anion such as N, N-dimethylanilinium tetrakis (pentafluorophenyl) -borate or tris (pentafluorophenyl) borate is used. In another embodiment, two L groups may be linked to form a dianionic leaving group such as an oxalate.

In another embodiment of the invention, each L' is independently selected from the group consisting of ethers, thioethers, amines, nitriles, imines, pyridines and phosphines, preferably ethers.

In any of the embodiments of the invention described herein, M is preferably a group 4 metal, preferably Zr or Hf.

In any of the embodiments of the invention described herein, E and/or E is preferably carbon.

Preferably in any embodiment of the invention described herein, R⁶And R⁷Are the same.

In any of the embodiments of the invention described herein, R¹，R³，R⁴，R⁵And R¹⁷May each contain no more than 30 carbon atoms.

In any of the embodiments of the invention described herein, E is carbon and R¹And R¹⁷Independently selected from phenyl substituted with 0, 1,2,3,4 or 5 substituents selected from F, Cl, Br, I, CF₃，NO₂Alkoxy, dialkylamino, hydrocarbyl, and substituted hydrocarbyl (having 1-10 carbons).

In a preferred embodiment of the invention, the pyridyldiamido transition goldThe complex is represented by the formula (A) and R⁶And R⁷At least one of (a) is a group having 1 to 100 (preferably 6 to 40, preferably 7 to 30) carbons.

In a preferred embodiment of the invention, the pyridyldiamido transition metal complex is represented by formula (A) above, and M is a group 4 metal, preferably Zr or Hf, preferably Hf.

In a preferred embodiment of the invention, the pyridyldiamido transition metal complex is represented by formula (B) above, and M is a group 4 metal, preferably Zr or Hf, preferably Hf.

In a preferred embodiment of the present invention, the pyridyldiamido transition metal complex is represented by the above formula (A), and G²Is oxygen, and G¹And G³Is a carbon atom, which is bonded to each other by 2 to 6 additional atoms to form a ring structure.

In a preferred embodiment of the present invention, the pyridyldiamido transition metal complex is represented by the above formula (B), and G²Is oxygen, and G¹And G³Is a carbon atom, which is bonded to each other by 2 to 6 additional atoms to form a ring structure.

In a preferred embodiment of the present invention, the pyridyldiamido transition metal complex is represented by the above formula (A), and G²Is nitrogen, and G¹And G³Is a carbon atom, which is bonded to each other by 2 to 6 additional atoms to form a ring structure.

In a preferred embodiment of the present invention, the pyridyldiamido transition metal complex is represented by the above formula (B), and G²Is nitrogen, and G¹And G³Is a carbon atom, which is bonded to each other by 2 to 6 additional atoms to form a ring structure.

In a preferred embodiment of the present invention, the pyridyldiamido transition metal complex is represented by the above formula (A), and G²Is sulfur, and G¹And G³Is a carbon atom, which is bonded to each other by 2 to 6 additional atoms to form a ring structure.

In the inventionIn a preferred embodiment, the pyridyldiamido transition metal complex is represented by formula (B) above, and G²Is sulfur, and G¹And G³Is a carbon atom, which is bonded to each other by 2 to 6 additional atoms to form a ring structure.

In a preferred embodiment of the present invention, the pyridyldiamido transition metal complex is represented by the above formula (C), and Q³Is C (H), R1 is 2, 6-diisopropylphenyl, and R¹⁷Is phenyl.

In a preferred embodiment of the present invention, the pyridyldiamido transition metal complex is represented by the above formula (D), R⁶Is H, R⁷Is a group containing 1 to 100 (preferably 6 to 40, preferably 7 to 30) carbons, M is a group 4 metal (preferably Zr or Hf, preferably Hf), and E is carbon.

In a preferred embodiment of the present invention, the pyridyldiamido transition metal complex is represented by the above formula (A), and R¹Is a2, 6-disubstituted aryl group, where the substituent is selected from isopropyl, 3-pentyl, or an alicyclic hydrocarbon containing from 4 to 20 carbons.

In a preferred embodiment of the present invention, the pyridyldiamido transition metal complex is represented by the above formula (A), and Q¹Is three atoms of a pyridine, imidazole, tetrahydrofuran, dioxane, dihydrothiazole, oxazolethiol, tetrahydropyran, dihydrooxazole or phosphinite group which is substituted in adjacent positions.

In a preferred embodiment of the present invention, the pyridyldiamido transition metal complex is represented by the above formula (A), and R²Is CH (aryl) and the aryl group contains 7 to 20 carbon atoms.

In another aspect of the invention, different methods of synthesizing the complexes described herein are provided.

The pyridyldiamide ligands described herein are typically prepared in multiple steps. One key step involves the preparation of a suitable "linking" group that contains both an aryl boronic acid (or acid ester) and an amine group. Examples thereof include compounds of the following general formula: 7- (boronic acid) -2, 3-dihydro-1H-indene-1- (amine), 7- (boronate) -2, 3-dihydro-1H-1- (amine), 7- (boronic acid) -1,2,3, 4-tetrahydronaphthalen-1- (amine), 7- (boronate) -1,2, 34-tetrahydronaphthalen-1- (amine), which includes different boronic acids, boronates and amines. The linking group can be prepared from an aryl halide precursor containing amine functionality in high yield as follows: the amine group is first deprotonated with 1.0 molar equivalents of n-BuLi, followed by a metal exchange reaction of the aryl halide with t-BuLi, and then reacted with a boron-containing reagent. This amine-containing linkage is then coupled with a suitable pyridine-containing material such as 6-bromo-2-pyridinecarboxaldehyde. This coupling step typically uses less than 5 mol% loading of a metal catalyst (e.g., Pd (PPh)₃)₄). After this coupling step, the new derivative (which may be described as amine-linked-pyridine-aldehyde) is then reacted with a second amine in a condensation reaction to produce the imine derivative amine-linked-pyridine-imine. This can then be reduced to the pyridyldiamine ligand by reaction with a suitable aryl anion, alkyl anion or hydride source. When aryl lithium or alkyl lithium reagents are used, the reaction is typically carried out in an ether solvent at a temperature of-100 ℃ to 50 ℃. When sodium cyanoborohydride is used, this reaction is generally carried out in methanol at reflux.

Preparation of pyridyldiamido metal complexes from pyridyldiamines can be carried out using typical proton exchange and methylation reactions. In a proton exchange reaction, the pyridyldiamide is reacted with a suitable metal reactant to produce a pyridyldiamido metal complex. Suitable metal reactants are characterized by a basic leaving group that will accept a proton from a pyridyldiamine and then typically be removed and disposed of from the product. Suitable metal reactants include, but are not limited to, HfBn₄(Bn＝CH₂Ph)，ZrBn₄，TiBn₄，ZrBn₂Cl₂(OEt₂)，HfBn₂Cl₂(OEt₂)₂，Zr(NMe₂)₂Cl₂(dimethoxyethane), Hf (NMe)₂)₂Cl₂(dimethoxyethane), Hf (NMe)₂)₄And Hf (NEt)₂)₄. Pyridyldiamido metal complex (thereof)Containing a metal-chloride group, such as PDA dichloride complex in scheme 1 below) can be alkylated by reaction with a suitable organometallic reagent. Suitable reagents include organolithium and organomagnesium, and grignard reagents. The alkylation is usually carried out in an ether or hydrocarbon solvent or solvent mixture at a temperature of usually-100 ℃ to 50 ℃.

Scheme 1

Here, in scheme 1, R¹，R²，R³，R⁴Independently selected from H, hydrocarbyl (e.g., alkyl, aryl), substituted hydrocarbyl (e.g., heteroaryl), and silyl, and R_nRepresents hydrogen, hydrocarbyl, or substituted hydrocarbyl which may combine to form a polycyclic aromatic ring and n is 1,2,3 or 4.

Another route to pyridyldiamido and other complexes of interest as catalysts involves the insertion of unsaturated molecules into covalent metal-carbon bonds where the covalently bonded group is part of a multidentate ligand structure, such as that described by Boussie et al in US 6750345. The unsaturated molecule will typically have a carbon-X double or triple bond, where X is a group 14 or group 15 or group 16 element. Examples of unsaturated molecules include alkenes, alkynes, imines, nitriles, ketones, aldehydes, amides, formamides, carbon dioxide, isocyanates, thioisocyanates, and carbodiimides. The following are examples showing the insertion reaction, which include benzophenone and N, N-dimethylformamide.

Activating agent

After the complexes have been synthesized, the catalyst systems can be formed by combining them with activators in any manner known in the literature, including loading them for slurry or gas phase polymerization. The catalyst system may also be added to or produced from solution polymerization or bulk polymerization (in monomer). The catalyst system typically comprises the above-described complex and an activator such as an alumoxane or a non-coordinating anion. Activation may be by using aluminoxane solutions, including methylaluminoxane (referred to as MAO) and modified MAO (referred to herein as MMAO) containing some higher alkyl groups to improve solubility. Particularly useful MAO is available from Albemarle, typically as a 10 wt% solution in toluene. The catalyst system used in the present invention preferably uses an activator selected from aluminoxanes such as methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and the like.

When an alumoxane or modified alumoxane is used, the complex-to-activator molar ratio is from about 1:3000 to 10: 1; alternatively 1:2000-10: 1; optionally 1:1000-10: 1; alternatively, 1:500-1: 1; alternatively 1:300-1: 1; alternatively 1:200-1: 1; alternatively 1:100 to 1: 1; alternatively 1:50-1: 1; alternatively 1:10-1: 1. When the activator is an alumoxane (modified or unmodified), some embodiments select a maximum amount of activator that exceeds 5000 times the mole of the catalyst precursor (per metal catalytic site). The preferred minimum activator-complex ratio is 1:1 molar ratio.

Activation can also be carried out using non-coordinating anions of the type described in EP277003A1 and EP277004A1 (referred to as NCA). NCA may be in the form of an ion pair using, for example, [ DMAH ]]⁺[NCA]^-Wherein the N, N-Dimethylaniline (DMAH) cation reacts with a basic leaving group on the transition metal complex to form a transition metal complex cation and [ NCA]^-. The cation in the precursor may alternatively be a trityl group. Alternatively, the transition metal complex may be reacted with a neutral NCA precursor such as B (C)₆F₅)₃Reaction, which extracts the anionic groups in the complex to form the activated species. Useful activators include N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (i.e., [ PhNMe ]₂H]B(C₆F₅)₄) And N, N-dimethylanilinium tetrakis (heptafluoronaphthyl) borate, where Ph is phenyl and Me is methyl.

Further preferred activators useful herein include those described in US7247687 at column 169, line 50 to column 174, line 43, especially column 172, line 24 to column 173, line 53.

In one embodiment of the invention described herein, the non-coordinating anion activator is represented by the following formula (1):

(Z)d⁺(A^d-) (1)

wherein Z is (L-H) or a reducible Lewis acid; l is a neutral Lewis base; h is hydrogen and (L-H)⁺Is a bronsted acid; a. the^d-A non-coordinating anion having a charge d^-(ii) a And d is an integer from 1 to 3.

When Z is (L-H), so that the cationic component is (L-H)_d ⁺When used, the cationic component may include a Bronsted acid such as a protonated Lewis base capable of protonating a moiety such as an alkyl or aryl group from a catalyst precursor to produce a cationic transition metal species, or the activating cation (L-H)_d ⁺Is a bronsted acid capable of donating a proton to the catalyst precursor, producing transition metal cations including ammonium, oxonium, phosphonium, silylium and mixtures thereof, or ammonium from: methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N-dimethylaniline, methyldiphenylamine, pyridine, p-bromon, N-dimethylaniline, p-nitro-N, N-dimethylaniline, phosphonium from the following: triethylphosphine, triphenylphosphine and diphenylphosphine, oxonium derived from ethers, such as dimethyl ether diethyl ether, tetrahydrofuran and dioxane, sulfonium derived from sulfides, such as diethyl sulfide and tetrahydrothiophene, and mixtures thereof.

When Z is a reducible Lewis acid, it may be represented by the formula: (Ar)₃C⁺) Where Ar is aryl or heteroatom-substituted aryl, or C₁-C₄₀A hydrocarbyl group, the reducible lewis acid being represented by the formula: (Ph)₃C⁺) Ph is phenyl or phenyl substituted by hetero atoms, and/or C₁-C₄₀A hydrocarbyl group. In one embodimentThe reducible lewis acid is a triphenylcarbenium ion.

Anionic component A^d-Examples of (c) include compounds having the formula [ M^k+Q_n]^d-Wherein k is 1,2 or 3; n is 1,2,3,4, 5 or 6, or 3,4, 5 or 6; n-k ═ d; m is an element of group 13 of the periodic table of the elements, or boron or aluminum, and Q is independently a hydride, bridged or unbridged dialkylamido, halide, alkoxylate, aryloxide, hydrocarbyl group, said Q having up to 20 carbon atoms and defining that no more than one occurrence of Q is a halide, and both Q groups may form a ring structure. Each Q may be a fluorinated hydrocarbon group having 1 to 20 carbon atoms, or each Q is a fluorinated aryl group, or each Q is a pentafluoroaryl group. Suitably A^d-Examples of components also include diboron compounds disclosed in U.S. patent No.5447895, which is incorporated herein by reference in its entirety.

In any of the embodiments of the NCA represented by formula 1 above, the anionic component A^d-Is of the formula [ M x k + Q x n]d-, wherein k is 1,2 or 3; n is 1,2,3,4, 5 or 6 (or 1,2,3 or 4); n-k ═ d; m is boron; and Q is independently selected from hydride, bridged or unbridged dialkylamides, halogens, alkoxylates, oxidized aryls, hydrocarbyl, said Q having up to 20 carbon atoms and Q defined at no more than 1 is halogen.

The present invention also relates to a process for polymerizing olefins comprising contacting an olefin (e.g., propylene) with the above-described catalyst complex and an NCA activator represented by formula (2):

R_nM^**(ArNHal)_4-n(2)

where R is a monoanionic ligand; m^**Is a group 13 metal or a nonmetal; ArNHal is a halogenated nitrogen-containing aromatic ring, polycyclic aromatic ring, or aromatic ring assembly in which two or more rings (or fused ring systems) are linked directly to each other or together; and n is 0, 1,2 or 3. Typically the NCA comprising the anion of formula 2 further comprises a suitable cation which does not substantially interfere with the ionic catalyst complex formed from the transition metal compound, or the cationZ is above_d ⁺。

In any of the embodiments of the anion-containing NCA shown in formula 2 above, R is selected from C₁-C₃₀A hydrocarbyl group. In one embodiment, C₁-C₃₀The hydrocarbyl group may be substituted with one or more of the following: c₁-C₂₀Hydrocarbyl, halide, hydrocarbyl-substituted organometalloid, dialkylamide, alkoxy, aryloxy, alkylthio, arylthio, alkylphosphorus, arylphosphorous, or other anionic substituent; a fluoride compound; bulky alkoxylates, where bulky denotes C₄-C₂₀A hydrocarbyl group; - -SRa, - -NRa2 and- -PRa2, where each Ra is independently a monovalent C₄-C₂₀A hydrocarbyl group comprising a molecular volume greater than or equal to the molecular volume of the isopropyl substituent, or C₄-C₂₀A hydrocarbyl-substituted organometalloid having a molecular volume greater than or equal to the molecular volume of an isopropyl substituent.

In any of the embodiments of the anion-containing NCA shown in formula 2 above, the NCA further comprises a cation comprising the formula: (Ar)₃C⁺) A reducible Lewis acid as shown, where Ar is aryl or heteroatom-substituted aryl, and/or C₁-C₄₀A hydrocarbyl group, or formula: (Ph)₃C⁺) A reducible Lewis acid as shown, where Ph is phenyl or phenyl substituted with one or more heteroatoms, and/or C₁-C₄₀A hydrocarbyl group.

In any of the embodiments of the anion-containing NCA represented by formula 2 above, the NCA may further comprise formula (L-H)_d ⁺A cation as shown, wherein L is a neutral lewis base; h is hydrogen; (L-H) is a Bronsted acid; and d is 1,2 or 3, or (L-H)_d ⁺Is a Bronsted acid selected from the group consisting of ammonium, oxonium, phosphonium, silyl cations and mixtures thereof.

Additional examples of useful activators include those disclosed in U.S. patent nos. 7297653 and 7799879, which are incorporated herein by reference in their entirety.

In one embodiment, the activators useful herein comprise a salt of a cationic oxidizing agent and a noncoordinating, compatible anion represented by formula (3):

(OX^e+)_d(A^d-)_e(3)

wherein OX^e+Is a cationic oxidant having a charge e +; e is 1,2 or 3; d is 1,2 or 3; and A^d-Is a non-coordinating anion, having a charge d- (as further described above). Examples of cationic oxidizing agents include: ferrocenium salts, hydrocarbon-substituted ferrocenium salts, Ag⁺Or Pb⁺²。A^d-Suitable embodiments include tetrakis (pentafluorophenyl) borate.

Activators useful in the catalyst systems herein: trimethylammonium tetrakis (perfluoronaphthyl) borate, N, N-dimethylanilinium tetrakis (perfluoronaphthyl) borate, N, N-diethylanilinium tetrakis (perfluoronaphthyl) borate, triphenylcarbenium tetrakis (perfluoronaphthyl) borate, trimethylammonium tetrakis (perfluorobiphenyl) borate, N, N-dimethylanilinium tetrakis (perfluorobiphenyl) borate, triphenylcarbenium tetrakis (perfluorobiphenyl) borate, and the types disclosed in U.S. Pat. No.7297653, which are fully incorporated herein by reference.

Suitable activators also include: n, N-dimethylanilinium tetrakis (perfluoronaphthyl) borate, N, N-dimethylanilinium tetrakis (perfluorobiphenyl) borate, 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 (perfluorophenyl) borate, [ Ph ] Ph₃C⁺][B(C₆F₅)₄ ^-]，[Me₃NH⁺][B(C₆F₅)₄ ^-](ii) a 1- (4- (tris (pentafluorophenyl) borate) -2,3,5, 6-tetrafluorophenyl) pyridinium; and tetrakis (pentafluorophenyl) borate, 4- (tris (pentafluorophenyl) borate) -2,3,5, 6-tetrafluoropyridine.

In one embodiment, the activator comprises a triarylcarbonium (e.g., triphenylcarbonium tetraphenylborate, triphenylcarbonium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis- (2,3,4, 6-tetrafluorophenyl) borate, triphenylcarbonium tetrakis (perfluoronaphthyl) borate, triphenylcarbonium tetrakis (perfluorobiphenyl) borate, triphenylcarbonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate).

In one embodiment, two NCA activators may be used in the polymerization, and the molar ratio of the first NCA activator to the second NCA activator may be any ratio. In one embodiment, the molar ratio of the first NCA activator to the second NCA activator is from 0.01:1 to 10000:1, alternatively from 0.1:1 to 1000:1, alternatively from 1:1 to 100: 1.

In one embodiment of the invention, the NCA activator-catalyst ratio is 1:1 molar ratio, alternatively 0.1:1 to 100:1, alternatively 0.5:1 to 200:1, alternatively 1:1 to 500:1 or 1:1 to 1000: 1. In one embodiment, the NCA activator-catalyst ratio is from 0.5:1 to 10:1, alternatively from 1:1 to 5: 1.

In one embodiment, the catalyst compound may be combined with a combination of alumoxane and NCA (see, e.g., US5153157, US5453410, EP0573120B1, WO94/07928, and WO95/14044, which discuss the use of alumoxane in combination with ionizing activators, all of which are incorporated herein by reference).

In a preferred embodiment of the invention, when using NCA (e.g. ionic or neutral stoichiometric activator), the complex-activator molar ratio is typically from 1:10 to 1: 1; 1:10-10: 1; 1:10-2: 1; 1:10-3: 1; 1:10-5: 1; 1:2-1.2: 1; 1:2-10: 1; 1:2-2: 1; 1:2-3: 1; 1:2-5: 1; 1:3-1.2: 1; 1:3-10: 1; 1:3-2: 1; 1:3-3: 1; 1:3-5: 1; 1:5-1: 1; 1:5-10: 1; 1:5-2: 1; 1:5-3: 1; 1:5-5: 1; 1:1-1:1.2.

Alternatively, co-activators or chain transfer agents such as group 1,2 or 13 organometallic species (e.g., alkyl aluminum compounds such as tri-n-octyl aluminum) may also be used in the catalyst systems herein. The complex-co-activator molar ratio is 1:100-100: 1; 1:75-75: 1; 1:50-50: 1; 1:25-25: 1; 1:15-15: 1; 1:10-10: 1; 1:5-5: 1; 1:2-2: 1; 1:100-1: 1; 1:75-1: 1; 1:50-1: 1; 1:25-1: 1; 1:15-1: 1; 1:10-1: 1; 1:5-1: 1; 1:2-1: 1; 1:10-2:1.

Chain transfer agent

A "chain transfer agent" is any agent capable of undergoing hydrocarbyl and/or polymer group exchange between the coordination polymerization catalyst and the metal center of the chain transfer agent during the polymerization process. A "chain transfer agent" is any agent capable of transferring a growing polyolefin chain from one growing chain to another molecule or chain in a catalytic polymerization process, or transferring a portion of the growing chain to another portion of the same or separate chain. The chain transfer agent may be any desired chemical compound such as those disclosed in WO 2007/130306. Preferably the chain transfer agent is selected from group 2, 12 or 13 alkyl or aryl compounds; preferably zinc, magnesium or aluminium alkyl or aryl; preferably where the alkyl group is C₁-C₃₀Alkyl, optionally C₂-C₂₀Alkyl, optionally C_3-12Alkyl, typically independently selected from methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, cyclohexyl, phenyl, octyl, nonyl, decyl, undecyl and dodecyl; and diethyl zinc is particularly preferred here.

In a particularly useful embodiment, the present invention relates to a catalyst system comprising an activator, a catalyst complex as described herein and a chain transfer agent, wherein the chain transfer agent is selected from a group 2, 12 or 13 alkyl or aryl compound.

In a particularly useful embodiment, the chain transfer agent is selected from dialkylzinc or diarylzinc compounds, where the alkyl groups are independently selected from methyl, ethyl, propyl, butyl, isobutyl, t-butyl, pentyl, hexyl, and cyclohexyl. Alternatively, the chain transfer agent may be triphenylaluminum, where the phenyl group is substituted or unsubstituted.

In a particularly useful embodiment, the chain transfer agent is selected from trialkylaluminum compounds, where the alkyl groups are independently selected from methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, and cyclohexyl. Alternatively, the chain transfer agent may be triphenylaluminum, where the phenyl group is substituted or unsubstituted.

The process of the invention is characterized in one aspect in that the presence of the chain transfer agent increases the activity of the catalyst component by at least a factor of 2 or 3 or 4 or 5 or 6 relative to the activity in the absence of the chain transfer agent under the same conditions. Desirably, the activity of the catalyst component in the presence of a chain transfer agent (at any of the levels and conditions indicated herein) may be 90000 or 100000 or 150000g/mmol/h/bar to 200000 or 250000 or 300000 or 400000g/mmol/h/bar, with desirable reagent characteristics. In the absence of chain transfer agent, the catalyst component typically has an activity of less than 90000 or 85000 or 80000 or 50000g/mmol/h/bar, but typically at least 50 or 100 g/mmol/h/bar.

In another embodiment, the Mw/Mn (i.e., molecular weight distribution ("MWD")) of a polymer produced using CTA in a batch polymerization process is lower than the MWD of a polymer produced under the same conditions in the absence of a chain transfer agent, preferably the MWD is at least 30% lower, preferably at least 50% lower, preferably at least 100% lower.

Useful chain transfer agents are generally present in an amount of from 10 or 20 or 50 or 100 equivalents to 600 or 700 or 800 or 1000 equivalents relative to the catalyst component. Alternatively, the chain transfer agent ("CTA") is present in a catalyst complex-CTA molar ratio of about 1:3000 to 10: 1; alternatively 1:2000-10: 1; optionally 1:1000-10: 1; alternatively 1:500-1: 1; alternatively 1:300-1: 1; alternatively 1:200-1: 1; alternatively 1:100 to 1: 1; alternatively 1:50-1: 1; alternatively 1:10-1: 1.

Useful chain transfer agents include diethyl zinc, tri-n-octyl aluminum, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, diethyl aluminum chloride, dibutyl zinc, di-n-propyl zinc, di-n-hexyl zinc, di-n-pentyl zinc, di-n-decyl zinc, di-n-dodecyl zinc, di-n-tetradecyl zinc, di-n-hexadecyl zinc, di-n-octadecyl zinc, diphenyl zinc, diisobutyl aluminum hydride, diethyl aluminum hydride, di-n-octyl aluminum hydride, dibutyl magnesium, diethyl magnesium, dihexyl magnesium, and triethyl boron.

Carrier

The complexes described herein may be supported by any method effective to support other coordination catalyst systems (with or without activators), effectively meaning that the catalysts prepared can be used to oligomerize or polymerize olefins in a heterogeneous process. The procatalyst, activator, co-activator (if desired), suitable solvent and support may be added in any order or simultaneously. Typically, the complex and activator may be combined in a solvent to form a solution. The carrier is then added and the mixture is stirred for 1 minute to 10 hours. The total solution volume may be greater than the pore volume of the support, but in some embodiments, the total solution volume is limited to less than the volume required to form a gel or slurry (about 90% to 400%, preferably about 100% to 200% of the pore volume). After stirring, residual solvent is removed under vacuum, typically at ambient temperature and for 10-16 hours. But greater or lesser times and temperatures are possible.

The complex may also be supported in the absence of an activator; in that case, the activator (and co-activator if desired) is added to the liquid phase of the polymerization process. In addition, two or more different complexes may be placed on the same support. Likewise, two or more activators or one activator and co-activator may be disposed on the same support.

Suitable solid particulate carriers typically comprise a polymer or a refractory oxide material, each of which is preferably porous. Preferably any support material having an average particle size of greater than 10 μm is suitable for use in the present invention. Different embodiments select porous support materials such as for example talc, inorganic oxides, inorganic chlorides such as magnesium chloride and resinous support materials such as polystyrene polyolefins or polymer compounds or any other organic support material etc. Some embodiments select inorganic oxide materials as support materials, including group-2, -3, -4, -5, -13, or-14 metal or non-metal oxides. Some embodiments select the catalyst support material to include silica, alumina, silica-alumina and mixtures thereof. Other inorganic oxides may be used alone or in combination with silica, alumina or silica-alumina. These are magnesia, titania, zirconia, and the like. Lewis acidic materials such as montmorillonite and similar clays can also serve as a support. In this case, the support may optionally double as an activator component; however, additional activators may also be used.

The support material may be pretreated by any number of methods. For example, the inorganic oxide may be calcined, chemically treated with a hydroxylating agent such as an aluminum alkyl group, or the like, or both.

As mentioned above, polymeric carriers will also be suitable according to the present invention, see for example the specifications of WO95/15815 and US 5427991. The disclosed methods can be used with the catalyst complexes, activators or catalyst systems of the present invention to adsorb or absorb them onto the polymeric support, particularly if composed of porous particles, or can be chemically bonded onto or into the polymer chains through functional groups.

Typical surface areas of useful supports are from 10 to 700m²Pore volume 0.1-4.0cc/g and average particle size 10-500 μm. Some embodiments select a surface area of 50 to 500m²(iii) a pore volume of 0.5 to 3.5cc/g, or an average particle size of 20 to 200 μm. Other embodiments select a surface area of 100-400m²Pore volume 0.8-3.0cc/g and average particle size 30-100 μm. Typical pore sizes for useful carriers are 10-1000 angstroms, alternatively 50-500 angstroms or 75-350 angstroms.

The catalyst complexes described herein are typically supported at a loading level of 10 to 100 micromoles of complex per gram of solid support; optionally 20-80 micromoles of complex per gram of solid support; or 40-60 micromoles of complex per gram of support deposited on the support. However, larger or smaller values may be used, with the total amount of solid complex being limited to not exceeding the pore volume of the support.

Polymerisation

The catalyst complexes of the present invention are useful for polymerizing unsaturated monomers which are conventionally known to undergo metallocene catalyzed polymerizations such as solution, slurry, gas phase and high pressure polymerizations. Typically one or more of the complexes described herein, one or more activators and one or more monomers are contacted to produce a polymer. The complex may be supported and it will be particularly useful in known fixed bed, moving bed, fluid bed, slurry, solution or bulk modes of operation, which are carried out in single, series or parallel reactors.

One or more reactors in series or parallel may be used in the present invention. The complex, activator and co-activator if desired may be delivered to the reactor as a solution or slurry, respectively, activated on-line just prior to the reactor, or pre-activated, and pumped to the reactor as an activated solution or slurry. The polymerization is carried out in a single reactor run in which the monomer, comonomer, catalyst/activator/co-activator, optional scavenger and optional modifier are added continuously to a single reactor or a series of reactor runs in which the above components are added to each of two or more reactors in series. The catalyst components may be added to the first reactor in series. The catalyst component may also be added to both reactors, with one component being added to the first reactor and the other component being added to the other reactor. In a preferred embodiment, the complex is activated in the presence of an olefin in the reactor.

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

The polymerization process used herein generally comprises contacting one or more olefin monomers with the complexes (and optional activators) described herein. In the present invention, olefins are defined to include both multiolefins (e.g., diolefins) and olefins having only one double bond. The polymerization can be homogeneous (solution or bulk polymerization) or heterogeneous (slurry-in a liquid diluent, or gas phase-in a gaseous diluent). In the case of heterogeneous slurry or gas phase polymerization, the complex and activator may be supported. Silica may be used as a support herein. Chain transfer agents (e.g., hydrogen or diethylzinc) may be used in the practice of the present invention.

The polymerization process of the present invention may be carried out under conditions preferably including a temperature of from about 30 ℃ to about 200 ℃, preferably from 60 ℃ to 195 ℃, preferably from 75 ℃ to 190 ℃. The process can be carried out at a pressure of from 0.05 to 1500 MPa. In a preferred embodiment the pressure is from 1.7MPa to 30MPa, or in another embodiment, especially under supercritical conditions, the pressure is from 15MPa to 1500 MPa.

Monomer

Monomers useful herein include olefins having from 2 to 40 carbon atoms, optionally from 2 to 12 carbon atoms (preferably ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene and dodecene) and optionally polyenes (e.g., dienes). Particularly preferred monomers include ethylene, and C₂-C₁₀Mixtures of alpha olefins such as ethylene-propylene, ethylene-hexene, ethylene-octene, propylene-hexene, and the like.

The complexes described herein are also particularly effective for the polymerization of ethylene, alone or with at least one other ethylenically unsaturated monomer such as C₃-C₂₀Alpha-olefins, and in particular C₃-C₁₂A combination of alpha-olefins. Likewise, the complexes of the invention are also particularly useful for polymerizing propylene, alone or with at least one other ethylenically unsaturated monomer such as ethylene or C₄-C₂₀Alpha-olefins, and in particular C₄-C₂₀A combination of alpha-olefins. Examples of preferred alpha-olefins include ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1, dodecene-1, 4-methylpentene-1, 3,5, 5-trimethylhexene-1, and 5-ethylnonene-1.

In some embodiments, the monomer mixture may also comprise up to 10 wt%, such as 0.00001 to 1.0 wt%, such as 0.002 to 0.5 wt%, such as 0.003 to 0.2 wt% of one or more dienes, based on the monomer mixture. Non-limiting examples of useful dienes include cyclopentadiene, norbornadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 1, 4-hexadiene, 1, 5-heptadiene, 1, 6-heptadiene, 6-methyl-1, 6-heptadiene, 1, 7-octadiene, 7-methyl-1, 7-octadiene, 1, 9-decadiene and 9-methyl-1, 9-decadiene.

Where olefins such as propylene are used, which produce short chain branching, the catalyst system can under the appropriate conditions produce stereoregular polymers or polymers having stereoregular sequences in the polymer chain.

In a preferred embodiment, the catalyst complex described herein, preferably of formula (A), (B), (C) or (D), preferably of formula (C) or (D), is used in any of the above polymerization processes to produce an ethylene homopolymer or copolymer or a propylene homopolymer or copolymer.

Scavenging agent

In some embodiments, when the complexes described herein are used, particularly when they are immobilized on a support, the catalyst system will additionally comprise one or more scavenging compounds. Here, the term scavenging compound refers to a compound that removes polar impurities from the reaction environment. These impurities adversely affect catalyst activity and stability. Typically, the scavenging compound will be an organometallic compound such as the group 13 organometallic compounds of U.S. Pat. Nos. 5153157, 5241025 and WO-A-91/09882, WO-A-94/03506, WO-A-93/14132 and WO 95/07941. Exemplary compounds include triethylaluminum, triethylborane, triisobutylaluminum, methylaluminoxane, isobutylaluminoxane, tri-n-octylaluminum, bis (diisobutylaluminum) oxide, modified methylaluminoxane. (useful Modified methylaluminoxanes include cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A) and those described in US 5041584). With a large volume or C attached to a metallic or non-metallic center₆-C₂₀Those scavenging compounds for linear hydrocarbyl substituents typically minimize adverse interactions with the active catalyst. Examples include triethylaluminum, but bulky compounds such as triisobutylaluminum, triisopentylaluminum, and long-chain linear alkyl-substituted aluminum compounds such as tri-n-hexylaluminum, tri-n-octylaluminum, or tri-n-dodecylaluminum are more preferred. When alumoxane is used as the activator, any amount in excess of that required for activation will scavenge impurities, and additionallyA scavenging compound may not be necessary. Alumoxanes also can be present in scavenging amounts with other activators such as methylalumoxane, [ Me ]₂HNPh]⁺[B(pfp)₄]^-Or B (pfp)₃(perfluorophenyl ═ pfp ═ C)₆F₅) Are added together.

In a preferred embodiment, two or more of the complexes described herein are combined with a chain transfer agent, such as diethyl zinc or tri-n-octyl aluminum, along with the monomers in the same reactor. Alternatively, one or more complexes are combined with another catalyst (e.g., a metallocene) and a chain transfer agent such as diethyl zinc or tri-n-octyl aluminum in the same reactor with the monomers.

Polymer product

Although the molecular weight of the polymers produced herein is influenced by reactor conditions (including temperature, monomer concentration and pressure, presence of chain terminators, etc.), the Mw of the homopolymer and copolymer products produced by the process of the present invention may be from about 1000 to about 2000000g/mol, alternatively from about 30000 to about 600000g/mol, alternatively from about 100000 to about 500000g/mol, as measured by gel permeation chromatography. Preferred polymers produced herein may be homopolymers or copolymers. In a preferred embodiment, the comonomer is present in up to 50 mol%, preferably from 0.01 to 40 mol%, preferably from 1 to 30 mol%, preferably from 5 to 20 mol%.

End use

Articles manufactured using the polymers produced herein may include, for example, molded article (e.g., containers and bottles, such as household containers, industrial chemical containers, personal care bottles, medical containers, fuel tanks and storage crockery, toys, sheets, tubes, pipelines) films, nonwovens, and the like. It should be understood that the above list of applications is exemplary only and is not intended to be limiting.

In another embodiment, the present invention relates to:

1. a pyridyldiamido transition metal complex (preferably for olefin polymerization) represented by the formula: (A) (B), (C) or (D):

wherein:

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

each R³⁰The radicals being independently hydrogen or C₁-C₁₀₀A hydrocarbyl or silyl group;

Q²is-NR¹⁷、-PR¹⁷Or oxygen, where R¹⁷Selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, silyl, and germyl;

R¹selected from hydrocarbyl, and substituted hydrocarbyl, or silyl;

R²is-E (R)¹²)(R¹³) -, and E is carbon, silicon or germanium;

y is selected from oxygen, sulfur and-E (R)⁶)(R⁷) And E is carbon, silicon or germanium;

l is an anionic leaving group, where the L groups may be the same or different, and any two L groups may be linked to form a dianionic leaving group;

n is 0, 1,2,3 or 4;

l' is a neutral lewis base; and

w is 0, 1,2,3 or 4.

2. The complex of paragraph 1 wherein M is Ti, Zr, or Hf.

3. The complex of paragraph 1 or 2, wherein R²Is selected from CH₂CH (aryl), CH (2-isopropylphenyl), CH (2, 6-dimethylphenyl), CH (2, 4-6-trimethylphenyl), CH (alkyl), CMe₂、SiMe₂、SiEt₂And SiPh₂。

4. The complex of paragraphs 1,2 or 3, wherein T is C, O, S or N.

5. Paragraphs 1,2,3 or4, wherein E and E are carbon and each R⁶、R⁷、R¹²And R¹³Is C₁-C₃₀Substituted or unsubstituted hydrocarbyl.

6. The complex of paragraphs 1,2,3,4 or 5, wherein E and E are carbon and each R⁶、R⁷、R¹²And R¹³Is C₆-C₃₀Substituted or unsubstituted aryl.

7. The complex of paragraphs 1,2,3,4, 5 or 6, wherein Q²is-NR¹⁷。

8. The complex of paragraphs 1,2,3,4, 5,6 or 7 wherein E and E are carbon and R¹And R¹⁷Independently selected from phenyl, substituted with 0, 1,2,3,4 or 5 substituents selected from: F. cl, Br, I, CF₃、NO₂Alkoxy, dialkylamino, hydrocarbyl and substituted hydrocarbyl having 1-10 carbons.

9. The complex of any of paragraphs 1-8, wherein Q¹Selected from:

here, theThe symbolic representation is connected to R²And an aromatic ring, and alkyl is an alkyl group.

10. The complex of any of paragraphs 1-9, wherein each L is independently selected from the group consisting of halide, alkyl, aryl, alkoxy, amide, hydride, phenoxy, hydroxy, silyl, allyl, alkenyl, trifluoromethanesulfonate, alkylsulfonate, arylsulfonate, and alkynyl; and each L' is independently selected from the group consisting of ethers, thioethers, amines, nitriles, imines, pyridines and phosphines.

11. The complex of any of paragraphs 1-10, wherein Q³Is CHCHCHCH, CHCH, CHN (alkyl), CH-S, CHC (alkyl) CH, C (alkyl) CHC (alkyl), CH-O or NO.

12. The complex of any of paragraphs 1-11, wherein the complex is represented by formula (a).

13. The complex of any of paragraphs 1-11, wherein the complex is represented by formula (B).

14. The complex of any of paragraphs 1-11, wherein the complex is represented by formula (C).

15. The complex of any of paragraphs 1-11, wherein the complex is represented by formula (D).

16. A catalyst system comprising an activator, optionally a chain transfer agent, and the complex of any of paragraphs 1-15.

17. The catalyst system of paragraph 16, wherein the activator comprises an alumoxane.

18. The catalyst system of paragraph 16, wherein the activator comprises a non-coordinating anion.

19. The catalyst system of paragraph 18, wherein the activator comprises one or more of:

20. A polymerization process comprising contacting one or more olefin monomers with the catalyst system of paragraphs 16-19.

21. The method of paragraph 20, wherein the monomer comprises ethylene.

22. The method of paragraph 20 or 21, wherein the monomer comprises propylene.

23. The method of paragraphs 20, 21 or 22, wherein the pyridyldiamido transition metal complex is supported.

24. The method of paragraph 23, wherein the support is silica.

25. The process of paragraphs 20-24 or the catalyst system of paragraphs 16-19 wherein a chain transfer agent, preferably a dialkylzinc and/or a trialkylaluminum, is present.

Experiment of

Preparation of N- [ (6-bromopyridin-2-yl) methyl ] -2, 6-diisopropylaniline.

A solution of 85.0g (457mmol) of 6-bromopyridine-2-carbaldehyde and 80.9g (457mmol) of 2, 6-diisopropylaniline in 1000ml of ethanol is refluxed for 8 h. The obtained solution was evaporated to dryness and the residue was recrystallized from 200ml of methanol. 113.5g (329mmol) of N- [ (1E) - (6-bromopyridin-2-yl) methylene group thus obtained were added under argon]33.16g (526mmol) of NaBH were added to 2, 6-diisopropylaniline₃CN, 9ml of acetic acid and 1000ml of methanol. This mixture was refluxed for 12h, then cooled to room temperature, poured into 1000ml of water, and the crude product was extracted with 3x200ml ethyl acetate. The combined extracts were dried over sodium sulfate and evaporated to dryness. The residue was purified by flash chromatography on silica gel 60(40-63um, eluent: hexane-ethyl acetate 10:1 vol). 104.4g (66%) of a yellow oil are obtained. Analytical calculation C₁₈H₂₃BrN₂: c, 62.25; h, 6.68; and N, 8.07. The following are found: c, 62.40; h, 6.87; and N, 7.90. 1H NMR (CDCl)₃): 7.50(m, 1H, 4-H in Py), 7.38(m, 1H, 5-H in Py), 7.29(m, 1H, 3-H in Py), 7.05-7.12(m, 3H, 3,4, 5-H in 2, 6-iPr)₂C₆H₃Medium), 4.18(s,2H，CH₂NH)，3.94(br.s，1H，NH)，3.33(sept，J＝6.8Hz，2H，CHMe₂)，1.23(d，J＝6.8Hz，12H，CHMe₂)。

preparing 7-bromoindan-1-ol.

To a mixture of 100g (746mmol) of indan-1-ol, 250ml (1.64mol) of N, N, N ', N' -tetramethylethylenediamine and 3000ml of pentane cooled to-20 deg.C was added 655ml (1.64mol) of a 2.5M solution of nBuLi in hexane. After the reaction mixture was refluxed for 12h, it was then cooled to-80 ℃. Further, 225ml (1.87mol) of 1, 2-dibromotetrafluoroethane was added, and the resulting mixture was allowed to warm to room temperature. The mixture was stirred for 12h, then 100ml water was added. The resulting mixture was diluted with 2000ml of water, and the organic layer was separated. The aqueous layer was extracted with 3x400ml toluene. The combined organic extracts were washed with Na₂SO₄Dried by drying and evaporation. The residue was distilled using a Kugelrohr apparatus with a boiling point of 120-. The yellow oil formed was dissolved in 50ml of triethylamine and the solution obtained was added dropwise to a stirred solution of 49.0ml (519mmol) of acetic anhydride and 4.21g (34.5mmol) of 4- (dimethylamino) pyridine in 70ml of triethylamine. The resulting mixture was stirred for 5min, then 1000ml water was added and stirring continued for 12 h. The reaction mixture was then extracted with 3x200ml ethyl acetate. The combined organic extracts were washed with Na₂CO₃Washing with an aqueous solution of Na₂SO₄Drying and evaporation drying. The residue was purified by flash chromatography on silica gel 60(40-63um, eluent: hexane-ethyl acetate 30:1 vol). The ester formed was dissolved in 1000ml of methanol, 50.5g (900mmol) of KOH were added and the mixture was refluxed for 3 h. The reaction mixture is then cooled to room temperature and poured into 4000ml of water. The crude product was extracted with 3x300ml dichloromethane. The combined organic extracts were washed with Na₂SO₄Dried by drying and evaporation. This gave 41.3g (26%) of a white crystalline solid. Is divided intoAnalysis and calculation of C₉H₉BrO: c50.73; H4.26. the following are found: c50.85; H4.48. 1HNMR (CDCl)₃): 7.34(d, J ═ 7.6Hz, 1H, 6-H); 7.19(d, J ═ 7.4Hz, 1H, 4-H); 7.12(dd, J ═ 7.6Hz, J ═ 7.4Hz, 1H, 5-H); 5.33(dd, J ═ 2.6Hz, J ═ 6.9Hz, 1H, 1-H), 3.18-3.26(m, 1H, 3-or 3 '-H), 3.09(m, 2H, 3, 3' -H); 2.73(m, 2H, 2, 2' -H).

Preparing 7-bromoindan-1-one.

To a solution of 37.9g (177mmol) of 7-bromoindan-1-ol in 3500ml of dichloromethane was added 194g (900mmol) of pyridinium chlorochromate. The resulting mixture was stirred at room temperature for 5h, then passed through a pad of silica gel (500ml) and the eluent was evaporated to dryness. 27.6g (74%) of a white crystalline solid were produced. Analytical calculation C₉H₇BrO: c51.22; H3.34. the following are found: c51.35; H3.41. 1H NMR (CDCl)₃)：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-N-phenyl-2, 3-dihydro-1H-indenyl-1-amine is prepared.

5.31g (28.0mmol) TiCl are added to a stirred solution of 10.4g (112mmol) aniline in 60ml toluene at room temperature in an argon atmosphere over a period of 30min₄. The resulting mixture was stirred at 90 ℃ for 30min, followed by the addition of 6.00g (28.0mmol) of 7-bromoindan-1-one. The resulting mixture was stirred at 90 ℃ for 10min, poured into 500ml of water, and the crude product was extracted with 3 × 100ml of ethyl acetate. Separating the organic layer over Na₂SO₄Dried and then evaporated to dryness. The residue was crystallized from 10ml of ethyl acetate at-30 ℃. The solid formed was isolated and dried in vacuo. Thereafter, it was dissolved in 100ml of methanol, and 2.70g (42.9mmol) of NaBH was added₃CN and 0.5ml of glacial acetic acid. The resulting mixture was refluxed for 3h under argon atmosphere. The resulting mixture was cooled to room temperature and then evaporated to dryness. The residue was diluted with 200ml water and the crude product was extracted with 3 × 50ml of ethyl acetate. The combined organic extracts were washed with Na₂SO₄Drying and evaporation drying. The residue was purified by flash chromatography on silica gel 60(40-63um, eluent: hexane-ethyl acetate-triethylamine ═ 100:10:1 by volume). This gave 5.50g (68%) of a yellow oil. Analytical calculation C₁₅H₁₄BrN: c, 62.52; h, 4.90; and (4) N4.86. The following are found: c, 62.37; h, 5.05; N4.62.1H NMR (CDCl)₃): 7.38(m, 1H, 6-H, in indan); 7.22(m, 3H, 3, 5-H, neutralized 4-H in phenyl, in indan); 7.15(m, 1H, 5-H, in indane); 6.75(m, 1H, 4-H, in indane); 6.69(m, 2H, 2,6-H in phenyl); 4.94(m, 1H, 1-H, in indan); 3.82(br.s, 1H, NH); 3.17-3.26(m, 1H, 3-or 3' -H, in indane); 2.92-2.99(m, 2H, 3' -or 3-H, in indane); 2.22-2.37(m, 2H, 2, 2' -H, in indane).

Preparation of N-phenyl-7- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) -2, 3-dihydro-1H-indenyl-1-amine.

To a solution of 2.50g (8.70mmol) of 7-bromo-N-phenyl-2, 3-dihydro-1H-indenyl-1-amine in 50ml of THF at-80 ℃ under argon was added 3.50ml (8.70mmol) of a 2.5M solution of nBuLi in hexane. The reaction mixture was then stirred at this temperature for 1 h. Further, 11.1ml (17.8mmol) of a 1.7M solution of tBuLi in pentane were added and the reaction mixture was stirred for 1 h. Then, 3.23g (17.4mmol) of 2-isopropoxy-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborolan was added. Thereafter the cooling bath was removed and the resulting mixture was stirred at room temperature for 1 h. To the resulting mixture was added 10ml of water, and the resulting mixture was evaporated to dryness. The residue was diluted with 200ml of water and the title product was extracted with 3 × 50ml of ethyl acetate. Combining the organic extractsIs extracted from Na₂SO₄Drying and evaporation drying. This gave 2.80g (96%) of a pale yellow oil. Analytical calculation C₂₁H₂₆BNO₂: c75.24; h7.82; and (4) N4.18. The following are found: c75.40; h8.09; and (4) N4.02. 1H NMR (CDCl)₃): 7.63(m, 1H, 6-H, in indane); 7.37-7.38(m, 1H, 4-H, in indan); 7.27-7.30(m, 1H, 5-H, in indan); 7.18(m, 2H, 3, 5-H in phenyl); 6.65-6.74(m, 3H, 2,4,6-H in phenyl); 5.20-5.21(m, 1H, 1-H, in indan); 3.09-3.17(m, 1H, 3-or 3' -H, in indane); 2.85-2.92(m, 1H, 3' -or 3-H, in indan); 2.28-2.37(m, 1H, 2-or 2' -H, in indane); 2.13-2.19(m, 1H, 2' -or 2-H, in indane); 1.20(s, 6-H, 4, 5-Me in BPin); 1.12(s, 6H, 4 ', 5' -Me in BPin).

Preparation of 7- (6- (((2, 6-diisopropylphenyl) amino) methyl) pyridin-2-yl) -N-phenyl-2, 3-dihydro-1H-indenyl-1-amine.

2.21g (21.0mmol) of Na was added₂CO₃A solution in a mixture of 80ml water and 25ml methanol was purged with argon for 30 min. The solution thus obtained was added to 2.80g (8.40mmol) of N-phenyl-7- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) -2, 3-dihydro-1H-indenyl-1-amine, 2.90g (8.40mmol) of N- [ (6-bromopyridin-2-yl) methyl ] l-ethyl]2, 6-diisopropylaniline, 0.48g (0.40mmol) Pd (PPh)₃)₄And 120ml of toluene. The mixture was stirred at 70 ℃ for 12h and then cooled to room temperature. The organic layer was separated and the aqueous layer was extracted with 3x50ml ethyl acetate. The combined organic extracts were washed with brine, over Na₂SO₄Drying and evaporation drying. The residue was purified by flash chromatography on silica gel 60(40-63um, eluent: hexane-ethyl acetate-triethylamine ═ 100: 5:1 by volume). This gave 2.00g (50%) of a yellow oil. Analytical calculation C₃₃H₃₇N₃: c83.33; h7.84; and N8.83. The following are found: c83.49; h7.66; n8.65.1H NMR(CDCl₃): 7.56-7.61(m, 3H, 6-H, in indan and 4.5-H, in Py); 7.46-7.51(m, 2H, 3, 5-H in phenyl); 7.14-7.16(m, 1H, 4-H, in indan); 7.08-7.12(m, 5H, 3-H in Py, 3,4, 5-H in 2, 6-diisopropylphenyl and 5-H in indan); 6.65(m, 1H, 4-H in phenyl); 6.53(m, 2H, 2,6-H in phenyl); 5.21-5.22(m, 1H, 1-H, in indan); 3.95-4.15(m, 4H, CH)₂NH and NH-phenyl and NH-2, 6-diisopropylphenyl); 3.31(sept, J ═ 6.8Hz, 2H, CH, in 2, 6-diisopropylphenyl); 3.16-3.24(m, 1H, 3-or 3' -H, in indane); 2.91-2.97(m, 1H, 3' -or 3-H, in indane); 2.21-2.37(m, 2H, 2, 2' -H, in indane); 1.19-2.21(m, 12H, CH)₃In 2, 6-diisopropylaniline).

Complex 1 was prepared.

Toluene (5mL) was added to 7- (6- (((2, 6-diisopropylphenyl) amino) methyl) pyridin-2-yl) -N-phenyl-2, 3-dihydro-1H-indenyl-1-amine (0.296g, 0.623mmol) and Hf (NMe)₂)₂Cl₂(dme) (0.267g, 0.623mmol) to form a clear colorless solution. The mixture was covered with aluminum foil loose and heated to 95 ℃ for 3 hours. The mixture was then evaporated to a solid and Et₂O (5mL) rinse to provide 0.432g of putative (pyridyldiamino) HfCl₂A complex compound. Dissolving it in CH₂Cl₂(5mL) neutralized and cooled to-50 ℃. Dimethylmagnesium (3.39mL, 0.747mmol) in Et was added dropwise₂O solution, and allowing the mixture to warm to ambient temperature. After 30 minutes, the volatiles were removed by evaporation and the residue was taken up in CH₂Cl₂(10mL) and filtered. The solution was concentrated to 2mL and pentane (4mL) was added. Cooling to-10 ℃ overnight provided colorless crystals, which were isolated and dried under reduced pressure. Yield 0.41g, 92%. 1H NMR (CD)₂Cl₂，400MHz)：8.00(t，1H)，6.85-7.65(13H)，5.06(d，1H)，4.91(dd，1H)，4.50(d，1H)，3.68(sept，1H)，3.41(m，1H)，2.85(m，1H)，2.61(sept，1H)，2.03(m，1H)，1.85(m，1H)，1.30(m，2H)，1.14(d，3H)，1.06(d，3H)，0.96(d，3H)，0.68(3，3H)，-0.48(s，3H)，-0.84(s，3H)。

Preparation of 8-bromo-1, 2,3, 4-tetrahydronaphthalen-1-ol.

To a mixture of 78.5g (530mmol) of 1,2,3, 4-tetrahydronaphthalen-1-ol, 160ml (1.06mol) of TMEDA and 3000ml of pentane, cooled to-20 ℃ was added dropwise 435ml (1.09mol) of a 2.5M solution of nBuLi in hexane. The resulting mixture was refluxed for 12 h. To the resulting mixture cooled to-80 ℃ was added 160ml (1.33mol) of 1, 2-dibromotetrafluoroethane, and the mixture was allowed to warm to room temperature, then stirred at this temperature for 12 h. After which 100ml of water was added. The resulting mixture was diluted with 2000ml of water, and the organic layer was separated. The aqueous layer was extracted with 3x400ml toluene. The combined organic extracts were washed with Na₂SO₄Dried by drying and evaporation. The residue was distilled using a Kugelrohr apparatus with a boiling point of 150-. The yellow oil formed was dissolved in 100ml of triethylamine and the solution obtained was added dropwise to a stirred solution of 71.0ml (750mmol) of acetic anhydride and 3.00g (25.0mmol) of DMAP in 105ml of triethylamine. The resulting mixture was stirred for 5min, then 1000ml of water was added and the resulting mixture was stirred for 12 h. The reaction mixture was then extracted with 3x200ml ethyl acetate. The combined organic extracts were washed with Na₂CO₃Washing with an aqueous solution of Na₂SO₄Drying and evaporation drying. The residue was purified by flash chromatography on silica gel 60(40-63um, eluent: hexane-ethyl acetate ═ 30:1 vol). The acetate formed was dissolved in 1500ml of methanol, 81.0g (1.45mol) of KOH were added and the mixture obtained was refluxed for 3 h. The reaction mixture is then cooled to room temperature and poured into 4000ml of water, and the title product is extracted with 3x300ml dichloromethane. The combined organic extracts were washed with Na₂SO₄Dried and then evaporated to dryness. 56.0g (47%) of a white crystalline solid were produced. Analytical calculation C₁₀H₁₁BrO：C52.89; H4.88. the following are found: c53.01; H4.75. 1H NMR (CDCl)₃): 7.38-7.41(m, 1H, 7-H); 7.03-7.10(m, 2H, 5, 6-H); 5.00(m, 1H, 1-H), 2.81-2.87(m, 1H, 4-or 4 '-H), 2.70-2.74(m, 1H, 4' -or 4-H), 2.56(br.s., 1H, OH), 2.17-2.21(m, 1H, 2-or 2 '-H), 1.74-1.79(m, 2H, 3, 3' -H).

Preparation of 8-bromo-3, 4-dihydronaphthalen-1 (2H) -one.

To a solution of 56.0g (250mmol) of 8-bromo-1, 2,3, 4-tetrahydronaphthalen-1-ol in 3500ml of dichloromethane 265g (1.23mol) of PCC was added. The resulting mixture was stirred at room temperature for 5h, then passed through a pad of silica gel (500ml) and evaporated to dryness. 47.6g (88%) of a colorless solid were produced. Analytical calculation C₁₀H₉BrO: c53.36; H4.03. the following are found: c53.44; H4.19. 1H NMR (CDCl)₃)：7.53(m，1H，7-H)；7.18-7.22(m，2H，5，6-H)；2.95(t，J＝6.1Hz，2H，4，4’-H)；2.67(t，J＝6.6Hz，2H，2，2’-H)；2.08(qv，J＝6.1Hz，J＝6.6Hz，2H，3，3’-H)。

Preparation of 8-bromo-N- (o-tolyl) -1,2,3, 4-tetrahydronaphthalen-1-amine.

25.3g (133mmol) of TiCl4 are added dropwise to a stirred solution of 57.1g (533mmol) of 2-methylaniline in 300ml of toluene at room temperature in an argon atmosphere over a period of 30 min. The resulting mixture was stirred at 90 ℃ for 30min, followed by the addition of 30.0g (133.0mmol) of 8-bromo-3, 4-dihydronaphthalen-1 (2H) -one. This mixture was stirred at 90 ℃ for 10min, poured into 500ml of water and the product extracted with 3 × 200ml of ethyl acetate. The combined organic extracts were washed with Na₂SO₄Drying and evaporation drying. The residue was recrystallized from 50ml of ethyl acetate. The solid obtained is dissolved in 600ml of methanol and 15.4g (244mmol) of NaBH are added under an argon atmosphere₃CN and 5ml of EtherAnd (4) acid. The resulting mixture was refluxed for 3h, then cooled to room temperature and evaporated to dryness. The residue was diluted with 500ml water and the crude product was extracted with 3x200ml ethyl acetate. The combined organic extracts were washed with Na₂SO₄Drying and evaporation drying. The residue was recrystallized from 400ml of methanol. This gave 33.2g (79%) of a yellow crystalline powder. Analytical calculation C₁₇H₁₈BrN: c64.57; h5.74; and (4) N4.43. The following are found: c64.69; h5.82; N4.55.1H NMR (CDCl)₃): 7.45(m, 1H, 7-H in tetralin); 7.19(m, 1H, 6-H in tetralin); 7.08-7.14(m, 3H, 5-H in tetrahydronaphthalene, and 3, 5-H in 2-methylphenyl); 6.86(m, 1H, 6-H in 2-methylphenyl); 6.68(m, 1H, 4-H in 2-methylphenyl); 4.78(m, 1H, 4-H in 2-methylphenyl); 3.51(br.s, 1H, NH); 2.86-2.92(m, 1H, 4-or 4' -H in tetralin); 2.72-2.81(m, 1H, 4' -or 4-H in tetralin); 2.30-2.34(m, 1H, 3-or 3' -H in tetralin); 2.06(s, 3H, CH)₃In 2-methylphenyl); 1.85-1.97(m, 1H, 3' -or 3-H in tetralin); 1.77-1.81(m, 1H, 2-or 2' -H in tetralin); 1.59-1.67(m, 1H, 2' -or 2-H in tetralin).

Preparation of 8- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) -N- (o-tolyl) -1,2,3, 4-tetrahydronaphthalen-1-amine.

To a solution of 30.8g (97.5mmol) (8-bromo-1, 2,3, 4-tetrahydronaphthalen-1-yl) (2-methylphenyl) amine in 500ml THF at-80 deg.C under argon atmosphere was added 39.0ml (97.5mmol) of a 2.5M solution of nBuLi in hexane. The resulting mixture was stirred at this temperature for 1h, then 125ml (200mmol) of a 1.7M solution of tBuLi in pentane were added. The resulting mixture was stirred at the same temperature for 1 h. Further, 36.3g (195mmol) of 2-isopropoxy-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborolan was added. Thereafter the cooling bath was removed and the resulting mixture was stirred at room temperatureStirring for 1 h. 10ml of water are then added and the mixture is evaporated to dryness. The residue was diluted with 500ml water and the title product was extracted with 3 × 200ml of ethyl acetate. The combined organic extracts were washed with Na₂SO₄Drying and evaporation drying. 24.8g (70%) of a yellow oil are produced. Analytical calculation C₂₃H₃₀BNO₂: c76.04; h8.32; and (3) N3.86. The following are found: c76.29; h8.60; and (3) N3.59. 1H NMR (CDCl)₃): 7.68-7.69(m, 1H, 7-H in tetrahydronaphthalene); 7.24-7.33(m, 3H, 5, 6-H, in tetrahydronaphthalene and 5-H, in 2-methylphenyl); 7.13(m, 1H, 3-H in 2-methylphenyl); 7.04(m, 1H, 6-H in 2-methylphenyl); 6.74-6.77(m, 1H, 4-H, in 2-methylphenyl); 5.38-5.39(m, 1H, 1-H in tetralin); 3.78(m, 1H, NH); 2.85-3.02(m, 2H, 4-H, in tetrahydronaphthalene); 2.21-2.26(m, 1H, 3-or 3' -H in tetralin); 2.12(s, 3H, CH)₃In 2-methylphenyl); 1.81-2.00(m, 3H, 3' -or 3-H and 2-H in tetralin); 1.20(s, 6H, CH)₃In BPin); 1.13(s, 6H, CH)₃In BPin).

Preparation of 8- (6- (((2, 6-diisopropylphenyl) amino) methyl) pyridin-2-yl) -N-phenyl-1, 2,3, 4-tetrahydronaphthalen-1-amine.

3.60g (34.0mmol) of Na₂CO₃The solution in a mixture of 150ml water and 45ml methanol was purged with argon for 30 min. The solution obtained was added to 5.00g (14.0mmol) of N- (2-methylphenyl) -8- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) -1,2,3, 4-tetrahydronaphthalen-1-amine, 4.85g (14.0mmol) of N- [ (6-bromopyridin-2-yl) methyl ] methyl]2, 6-diisopropylaniline, 0.80g (0.70mmol) Pd (PPh)₃)₄And 180ml of toluene. The mixture was stirred at 70 ℃ for 12h and then cooled to room temperature. The organic layer was separated and the aqueous layer was extracted with 3x50ml ethyl acetate. The combined organic extracts were washed with brine, over Na₂SO₄Drying, and evaporating to dry. The residue was purified by flash chromatography on silica gel 60(40-63um, eluent: hexane-ethyl acetate-triethylamine ═ 100:10:1 by volume). This gave 2.50g (36%) of a yellow oil. Analytical calculation C₃₅H₄₁N₃: c83.45; h8.20; and (8) N.34. The following are found: c83.69; h8.08; N8.13.1H NMR (CDCl)₃): 7.62-7.63(m, 1H, 7-H in tetrahydronaphthalene); 7.55-7.58(m, 1H, 4-H, in Py); 7.52-7.54(m, 1H, 3-H, in Py); 7.41-7.44(m, 1H, 6-H, in tetrahydronaphthalene); 7.37-7.39(m, 1H, 5-H, in Py); 7.15-7.16(m, 1H, 5-H in tetralin); 7.03-7.10(m, 4H, 3,4, 5-H, neutralized 5-H in 2, 6-diisopropylphenyl, in 2-methylphenyl); 6.93(m, 1H, 3-H in 2-methylphenyl); 6.70(m, 1H, 6-H in 2-methylphenyl); 6.59(m, 1H, 4-H in 2-methylphenyl); 5.35(m, 1H, 1-H in tetralin); 3.94-4.03(m, 2H, CH 2); 3.92-3.94(m, 1H, 4-or 4' -H in tetralin); 3.68-3.70(m, 1H, 4' -or 4-H in tetralin); 3.30(sept, J ═ 6.8Hz, 2H, CH, in 2, 6-diisopropylphenyl); 3.16-3.24(m, 1H, 3-or 3' -H in tetralin); 2.92-3.00(m, 1H, 3' -or 3-H in tetralin); 2.38-2.47(m, 1H, 2-or 2' -H in tetralin); 2.14-2.22(m, 1H, 2' -or 2-H in tetralin); 1.75(s, 3H, CH3, in 2-methylphenyl); 1.18-1.22(m, 12H, CH3, in 2, 6-diisopropylphenyl).

Preparation of complex 2.

Toluene (8mL) was added to 8- (6- (((2, 6-diisopropylphenyl) amino) methyl) pyridin-2-yl) -N-phenyl-1, 2,3, 4-tetrahydronaphthalen-1-amine (0.214g, 0.501mmol) and Hf (NMe)₂)₂Cl₂(dme) (0.214g, 0.501mmol) to form a light yellow solution. The mixture was covered with aluminum foil loose and heated to 95 ℃ for 3 hours. The mixture was then evaporated to a solid and Et₂O (5mL) rinse to provide 0.314g of putative (pyridyldiamido) HfCl₂A complex compound. Dissolving it in CH₂Cl₂(5mL) neutralized and cooled to-50 ℃. Dimethylmagnesium (1) was added dropwise53mL, 0.481mmol) of Et₂O solution, and the mixture is warmed to ambient temperature. After 30 minutes, the volatiles were removed by evaporation and the residue was taken up with CH₂Cl₂(8mL) and filtered. Evaporation afforded a solid which was washed with pentane (4mL) and dried under reduced pressure to afford complex 2. The yield was 0.28g, 79%. 1H NMR (CD)₂Cl₂，400MHz)：8.02(t，1H)，6.85-7.65(12H)，5.16(d，1H)，4.72(br，1H)，5.60(br d，1H)，3.68(sept，1H)，3.50(m，1H)，2.85(m，1H)，2.59(br，1H)，2.2(br，2H)，1.85(m，1H)，1.55(m，1H)，1.10(m，6H)，0.95(d，3H)，0.4(d，3H)，-0.63(s，3H)，-0.90(s，3H)。

Complex 3 (comparative) was prepared as described in US 8394902. Complex 4 (comparative) was prepared according to the general procedure described in US 8394902.

Polymerization examples

Table 1 shows the propylene polymerization data using complexes 1-2 (runs 1-4) and comparative complex 4 (runs 5-6) at a temperature of 70 ℃. From this data it is clear that the catalyst formed by activating complexes 1 and 2 has a significantly higher activity than the comparative example. On average, complex 1 produced a catalyst with 38% higher activity than complex 4. Similarly, complex 2 produced a catalyst with 42% higher activity than complex 4. The presence of tetralin groups also leads to an increase of the melting point of the polypropylene produced by about 2 ℃. This was observed by comparing the melting point of the polypropylene produced by complex 2 (runs 3-4) with the melting point of the polypropylene produced by complex 4 (runs 5-6).

Table 2 shows the propylene polymerization data using complexes 1-2 (runs 7-10) and comparative complexes 3 (runs 11) and 4 (runs 12-13) at a temperature of 85 ℃. From this data it is clear that the activity of the catalyst formed by activating complexes 1 and 2 is significantly higher than the comparative example. On average, complex 1 produced a catalyst with 49% higher activity than complex 4. Similarly, complex 2 produced a catalyst with 42% higher activity than complex 4. The catalysts of the invention from complexes 1 and 2 showed 252% and 236% increase in activity, respectively, relative to the catalyst produced by complex 3. The presence of tetralin groups also leads to an increase of the melting point of the polypropylene produced by about 2 ℃. This was observed by comparing the melting point of the polypropylene produced by complex 2 (runs 9-10) with the melting point of the polypropylene produced by complex 4 (runs 12-13). Similarly, the presence of indane groups also results in an increase in the melting point of the polypropylene produced by about 12 ℃. This was observed by comparing the melting point of the polypropylene produced by complex 1 (runs 7-8) with the melting point of the polypropylene produced by complex 3 (run 11).

General polymerization procedure

Unless otherwise indicated, propylene homopolymerization is carried out in parallel pressure reactors, as is common in US 6306658; US 6455316; US 6489168; WO 00/09255; and Murphy et al, j.am.chem.soc., 2003, 125, pp 4306-4317, each of which is hereby incorporated by reference in its entirety for the purposes of this application. Although the specific amounts, temperatures, solvents, reactants, reactant ratios, pressures and other variables often vary from one polymerization run to the next, a typical polymerization carried out in parallel pressure reactors is described below.

A pre-weighed glass vial insert and disposable stirring blade were mounted to each reaction vessel of a reactor containing 48 individual reaction vessels. Solvent (typically isohexane) was then added to reach a total reaction volume of 4mL, including subsequent additions. Propylene gas was introduced and the reactor vessels were heated to their set temperature. At this time, a solution of scavenger and/or cocatalyst and/or chain transfer agent, for example tri-n-octylaluminum in toluene (typically 100-1000nmol) is added.

The vessel contents were stirred at 800 rpm. An activator solution, typically 1.1 molar equivalent of dimethylanilinium tetrakis-pentafluorophenyl borate dissolved in toluene or 100-1000 molar equivalents of Methylaluminoxane (MAO) in toluene, is then injected into the reaction vessel along with 500 microliters of toluene, followed by a toluene solution of the catalyst (typically a 0.40mM toluene solution, typically 20-40 nanomoles of catalyst) and another aliquot of toluene (500 microliters). The equivalents are determined on the basis of molar equivalents relative to the moles of transition metal in the catalyst complex.

The reaction is then allowed to proceed until the reaction has reached a predetermined amount of pressure. Alternatively, the reaction may be carried out for a set amount of time. At this point, the reaction is quenched by pressurizing the vessel with compressed air. After the polymerization reaction, the glass vial insert containing the polymer product and solvent was removed from the pressure chamber and inserted into an atmospheric glove box and the volatile components were removed using a Genevac HT-12 centrifuge and a Genevac VC3000D vacuum evaporator (operating at elevated temperature and reduced pressure). The vial was then weighed to determine the yield of polymer product. The formed polymer was analyzed by fast GPC (see below) to determine the molecular weight, and by DSC (see below) to determine the melting point.

For determination of different molecular weight-related values by GPC, high temperature exclusion chromatography was performed using an automated "fast GPC" system, which is generally described in US 6491816; US 6491823; US 6475391; US 6461515; US 6436292; US 6406632; US 6175409; US 6454947; US 6260407; and US 6294388; each of which is incorporated herein in its entirety by reference for purposes of the united states. This apparatus has three 30cmx7.5mm linear columns in series, each containing Plgel10um, MixB. The GPC system used a polystyrene standard of 580-3390000 g/mol. The system was run at an eluent flow rate of 2.0mL/min and an oven temperature of 165 ℃.1, 2, 4-trichlorobenzene was used as the eluent. The polymer samples were dissolved in 1,2, 4-trichlorobenzene at concentrations of 0.1-0.9 mg/mL. 250uL of polymer solution was injected into the system. The polymer concentration in the eluate was monitored using an infrared absorption detector. The proposed molecular weights are relative to linear polystyrene standards and are uncorrected.

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

TABLE 1 homopolymerization of propylene. General conditions: 70 deg.C, 120psi C3, N, N-dimethylanilinium tetrakis (perfluorophenyl) borate (44nmol), tri-N-octylaluminum (300nmol) isohexane solvent.

TABLE 1 (continuation)

4	2	58	204	318	477235	250929	146.6
								5	4*	54	143	239	682952	359719	143.4
6	4*	64	163	229	692247	350672	145.1

Comparative example.

TABLE 2 homopolymerization of propylene. General conditions: 85 ℃, 120psi C3, N, N-dimethylanilinium tetrakis (perfluorophenyl) borate (44nmol), tri-N-octylaluminum (300nmol) isohexane solvent.

Comparative example.

In the claims, the following test methods should be used.

¹H NMR

1H NMR data were collected at 120 ℃ and should be done in a 5mm probe using a spectrometer with a 1H frequency of at least 400 MHz. Data were recorded using a maximum pulse width of 45 °, 8 seconds between pulses and a signal average of 120 transients. The spectral signals are integrated. The sample was dissolved in a heavy hydrogen containing dichloromethane at a concentration of 10-15 wt% prior to insertion into the spectrometer magnet. By combining the residual CHDCl prior to data analysis₂Resonance was set to 5.24ppm for reference spectra.

¹³C NMR

13C NMR data was collected at 120 ℃ using a spectrometer, and the 13C frequency was at least 75 MHz. A 90 degree pulse, adjusted collection time to produce digital resolution at 0.1-0.12Hz, a pulse collection delay time of at least 10 seconds, continuous broadband protons, decoupled using a scanning square wave module, no gating technique used during the entire collection time. Spectra are acquired and time averaged to provide a signal to noise level sufficient to measure the signal of interest. The sample was dissolved in a heavy hydrogen containing dichloromethane at a concentration of 10-15 wt% prior to insertion into the spectrometer magnet. The spectra were referenced by chemically shifting the heavy hydrogen containing dichloromethane solvent signal to 54ppm prior to data analysis.

Chain transfer agent

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Pyridyldiamido transition metal complexes, their production and use

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