CN107922441A

CN107922441A - The transition metal complex and its production and purposes of three tooth dianion CNN ligands

Info

Publication number: CN107922441A
Application number: CN201680044358.1A
Authority: CN
Inventors: J·R·哈格多恩; P·J·帕拉福克斯
Original assignee: Exxon Chemical Patents Inc
Current assignee: ExxonMobil Chemical Patents Inc
Priority date: 2015-06-30
Filing date: 2016-05-12
Publication date: 2018-04-17
Also published as: WO2017003565A1; EP3317288A1; EP3317288A4

Abstract

This document describes the new pyridinylamino transition metal complex composition for olefinic polymerization, it is characterised in that 7 yuan of chelate rings and cyclometallated hydrocarbyl radical.When being activated using common activator, these compositions form active olefin polymerization catalyst.These new carbon monoxide-olefin polymerics shown in this article are active especially for the polymer containing ethene is prepared for olefinic polymerization.

Description

The transition metal complex and its production and purposes of three tooth dianion CNN ligands

Inventor：John R.Hagadorn and Patrick J.Palafox

Priority

The EP Shens that the USSN 62/186,972 and August in 2015 that application claims are submitted on June 30th, 2015 are submitted on the 7th Please 15180120.6 priority and rights and interests.

Invention field

The present invention relates to three tooth dianion CNN ligands transition metal complex and be used to prepare such complex compound Intermediate and method.Tridentate ligand in these complex compounds is chelated with metal center, and for passing through carbanion respectively For the ring that coordination with amino group donor is formed, a five-membered ring and a heptatomic ring are formed.Transition metal complex can be used Make the catalyst of olefine polymerizing process.

Background of invention

The 4th group complex is prepared using pyridine radicals amine (pyridyl amine), it is useful in olefin polymerization Transition metal component, see, for example, US 2002/0142912, US6, in 900,321 and US 6,103,657, wherein ligand Have been used in the complex compound that wherein ligand is coordinated in the form of bidentate with transition metal atoms.

WO 2005/095469 is shown by two nitrogen-atoms (amino and a pyridine radicals) and an oxygen atom Use the catalyst compounds of tridentate ligand.

US 2004/0220050A1 and WO 2007/067965 discloses the 4th group 4 transition metal pyridinylamino (pyridylamide) (aryl is cloudy by two nitrogen (amino and a pyridine radicals) and a carbon for complex compound, wherein ligand Ion) donor is coordinated with three-tooth pattern.Amino group donor in these complex compounds is not with transition-metal coordination and forming heptatomic ring.

These complex compounds activation committed step be by alkene insertion catalyst precarsor metallo-aryl key in (Froese, Et al., R.D.J. J.Am.Chem.Soc., volume 2007,129, the 7831-7840 pages) to form active catalyst.Amino supplies Coordination of the body group in these complex compounds forms 5 yuan of rings rather than 7 yuan of rings.

US7,973,116B2 discloses the 4th race's pyridine radicals diaminourea of the catalytic component that can be used as olefine polymerizing process Complex compound.The characteristics of these complex compounds is three tooth dianion ligands, it is coordinated to metal center by three nitrogen donor groups.

Other bibliography interested include：1)Domski,G.J.；Rose,J.M.；Coates,G.W.；Bolig, A.D.；Brookhart,M.,“Living alkene polymerization:New methods for the precision Synthesis of polyolefins, " Prog.Polym.Sci., volume 2007,32, the 30-92 pages；2) Giambastiani,G.；Laconi,L.；Kuhlman,R.L.；Hustad,P.D.,“Imino-and amido- pyridinate d-block metal complexes in polymerization/oligomerization Catalysis, " the 5th chapter, Olefin Upgrading Catalysis by Nitrogen-based Metal Complexes I,Catalysis by Metal Complexes,Springer,2011；3)Vaughan,A；Davis,D.S.；Hagadorn, J.R.,“Industrial catalysts for alkene polymerization”,Comprehensive Polymer Science, volume 2012,3, the 20th chapter；4)Gibson,V.C.；Spitzmesser, S.K.Chem.Rev., 2003, the 103rd Volume, page 283；5)Britovsek,G.J.P.；Gibson,V.C.；Wass,D.F.；Angew.Chem.Int.Ed.,1999, Volume 38, page 428；6)WO 2010/037059；7)Boussie,Thomas R.et al."Nonconventional Catalysts for Isotactic Propene Polymerization in Solution Developed by Using High-Throughput-Screening Technologies"Angew.Chem.Int.Ed.2006,45,3278-3283；8) US 8,674,040；With 9) US 7,087,690.

There is still a need for there is the new catalyst complex of enhancing performance in olefin polymerization.

In addition, this area is required to produce the new catalyst of heavy polymer, bag at a temperature of high method Include highly crystalline polypropylene and the ethylene copolymer with alpha-olefin.

Summary of the invention

This document describes the new carbon monoxide-olefin polymeric for olefinic polymerization, it is characterised in that double with three teeth of metal coordination Anion ligand, it has a carbanion group, a neutral nitrogen donor groups and an anionic amino group.It is this Three teeth " CNN " ligand and metal-chelating with center neutral donor so that amino donor groups form 7 yuan of rings, and carbon is born Ionic group forms 5 yuan of rings.The presence of 7 yuan of rings is important, because it is obtained increases relevant time scale with polymer chain On complexing it is chiral (complex chiral) (C1 is symmetrical), it is for preparing isotactic poly (alpha-olefin) for example entirely with poly- third It is desired characteristics for the catalyst of alkene.When being activated using common activator, these compositions form active olefin polymerization Catalyst.These new carbon monoxide-olefin polymerics shown in this article are poly- containing ethene especially for preparing for olefinic polymerization Compound is active.

The present invention relates to the new transition metal complex with three tooth dianion CNN ligands.The invention further relates to by Heterocyclic amino group, pyridinylamino and the relevant transition metal complex that formula (I) represents：

Wherein：

M is the race of the 3rd, 4 or 5 metal；

Q is-(TT)-or-(TTT)-, wherein each T is the race's element of the substituted or unsubstituted 14th, 15 or 16 so that It forms 5- or 6- circle heterocycles together with "-C-N=C- " fragment；

R¹Alkyl (such as halocarbyl (halocarbyl), the halocarbyl of substitution, silicyl selected from alkyl, substitution Carbon-based (silylcarbyl)) and polar group；

Each R²And R³Independently selected from hydrogen, halogen, alkyl, substitution alkyl (such as halocarbyl, substitution halo carbon Base, silicyl are carbon-based) and polar group, and R²And R³It can engage to form ring；

Each R⁴、R⁵、R⁶And R⁷Independently selected from hydrogen, halogen, alkyl, substitution alkyl (such as halocarbyl, substitution Halocarbyl, silicyl are carbon-based) and polar group, and any adjacent R group can engage formation can be substituted or The ring of unsubstituted carbocyclic ring or heterocycle；

R³And R⁴It can engage to form ring；

J is the aromatic group containing 4-40 carbon atom, it is coordinated by carbanion donor and metal center；

Each X is anion leaving group, and wherein X group can be identical or different, and any two X group can connect Connect to form dianion leaving group；

Each L is neutral Lewis base, and any two L groups can engage to form bidentate lewis base；

X and L groups can be engaged covalently；

N is 1,2 or 3；

Y is 0,1 or 2；

Wherein n+y is not more than 4.

The invention further relates to prepare above-mentioned complex compound method, prepare for above-mentioned complex compound intermediate method, with And the method using above-mentioned complex compound olefin polymerization.

Attached drawing briefly describes

Fig. 1 be with C6D6~0.02M solution obtain and reference remaining C6D5H at δ 7.15ppm complex compound The 400MHz 1H-NMR spectrograms of B.

Fig. 2 shows the molecular structure of the complex compound B determined by the single crystal X-ray diffraction drawn with 30% thermal ellipsoid Two views.

Detailed description of the invention

Present specification describes transition metal complex.Term complex compound is used to describe wherein assistant ligand and central transition The molecule of metallic atom coordination.Ligand can pass through covalent bond and/or electronics supply coordination or middle key and transition-metal coordination. Usually using activator transition metal complex is activated with carry out its polymerization or oligomeric function, it is believed that activator due to from The commonly referred to as anionic group of leaving group is eliminated in transition metal and produces cation.

As used herein, periodic table of elements numbering plan is such as Chemical and Engineering News 1985, 63rd (5) are rolled up, the new charactery proposed of page 27.

As used herein, Me is that methyl, Et are that ethyl, Bu are that butyl, t-Bu are that the tert-butyl group, Pr are that propyl group, iPr are isopropyls Base, THF (also referred to as thf) are that tetrahydrofuran, Bn are that benzyl, Ph are that phenyl, RT are room temperatures.

Term " hydrocarbyl group (hydrocarbyl radical) ", " alkyl " and " hydrocarbyl group (hydrocarbyl Group) " whole interchangeably used herein.Equally, term " group (group) ", " group (radical) " and " substitution Base " is also used interchangeably herein.For the purpose of the disclosure, " hydrocarbyl group " is defined as C1-C100 groups, it can Can be aromatics or non-aromatic to be linear, branched or cricoid, and when being ring-type.

Substituted hydrocarbyl group is such group, wherein at least one hydrogen atom by least one functional group for example NR*₂、OR*、SeR*、TeR*、PR*₂、AsR*₂、SbR*₂、SR*、BR*₂、SiR*₃、GeR*₃、SnR*₃、PbR*₃Deng substitution, or Wherein at least one non-hydrocarbon atom or group are had been inserted into alkyl, such as-O- ,-S- ,-Se- ,-Te- ,-N (R*)-,= N- ,-P (R*)-,=P- ,-As (R*)-,=As- ,-Sb (R*)-,=Sb- ,-B (R*)-,=B- ,-Si (R*)₂-、-Ge (R*)₂-、-Sn(R*)₂-、-Pb(R*)₂- etc., wherein R* independently is alkyl or halocarbyl, and two or more R* can Substituted or unsubstituted saturation, part insatiable hunger and/or aromatic cyclic or polycyclic ring structure are formed to be bonded together.

Halocarbyl be wherein one or more alkyl hydrogen atoms by least one halogen (such as F, Cl, Br, I) or Halogen group elements (such as CF₃) substitution group.

Substituted halocarbyl group is such group, wherein at least one halocarbyl hydrogen or halogen atom by At least one functional group such as NR*₂、OR*、SeR*、TeR*、PR*₂、AsR*₂、SbR*₂、SR*、BR*₂、SiR*₃、GeR*₃、SnR *₃、PbR*₃Had been inserted into Deng substitution, or wherein at least one non-carbon or group in halocarbyl, such as-O- ,- S- ,-Se- ,-Te- ,-N (R*)-,=N- ,-P (R*)-,=P- ,-As (R*)-,=As- ,-Sb (R*)-,=Sb- ,-B (R*)-, =B- ,-Si (R*)₂-、-Ge(R*)₂-、-Sn(R*)₂-、-Pb(R*)₂- etc., wherein R* independently is alkyl or halocarbyl, bar Part is that at least one halogen atom is retained on original halocarbyl.The shape in addition, two or more R* can be bonded together Into substituted or unsubstituted saturation, part is undersaturated or aromatic cyclic or polycyclic ring structure.

The carbon-based group of silicyl (also referred to as silicyl is carbon-based) is that wherein silyl functional degree is bonded directly to refer to The group of fixed one or more atoms.Example includes SiH₃、SiH₂R*、SiHR*₂、SiR*₃、SiH₂(OR*)、SiH(OR*)₂、 Si(OR*)₃、SiH₂(NR*₂)、SiH(NR*₂)₂、Si(NR*₂)₃Deng wherein R* independently is alkyl or halocarbyl, and two A or more R* can be bonded together to be formed substituted or unsubstituted saturation, part is undersaturated or aromatic cyclic or Polycyclic ring structure.Carbon-based preferable silicyl is formula SiR*₃。

Polar group (polar radical) or polar group (polar group) are that wherein heteroatom functional degree is direct It is attached to the group for the one or more atoms specified.They individually include the hetero atom of periodic table of elements 13-17 races, or Including the period of element being connected by covalent bond or other interaction such as ionic bonds, Van der Waals force or hydrogen bond with other elements The hetero atom of Biao 13-17 races.The example of polar group include carboxylic acid, acyl halide, carboxylate, carboxylate, carboxylic acid anhydrides, aldehyde and its Chalcogen (the 14th race) analog, alcohol and phenol, ether, peroxide and hydroperoxides, carboxylic acid amide, hydrazides and acid imide, Amidine and other nitrogen analogs：Acid amides, nitrile, amine and imines, azo, nitro, other nitrogen compounds, sulfur acid, containing selenic acid, mercaptan, Sulfide, sulfoxide, sulfone, phosphine, phosphate (ester), other phosphorus compounds, silane, borine, borate (ester), aluminium alkane and aluminate (ester).Polar group further includes organic polymer carrier or inorganic carrier material such as aluminium oxide and silica.Polar group Preferred embodiment include NR*₂、OR*、SeR*、TeR*、PR*₂、AsR*₂、SbR*₂、SR*、BR*₂、SnR*₃、PbR*₃Deng wherein R* Alkyl as defined above, alkyl, halocarbyl or the substituted halocarbyl of substitution independently are, and two R* can be engaged Formed together substituted or unsubstituted saturation, part is undersaturated or aromatic cyclic or polycyclic ring structure.Polar group The most preferred example of group includes NR*₂And PR*₂。

Term " catalyst system " is defined to indicate that complex compound/activator pair.When " catalyst system " is used to describe in work During such pair before change, it represent non-activated catalyst complex (pre-catalyst) and activator and optionally help activation Agent is together.When it is for as description after the activation pairs, it represents the complex compound and activator or other electricity of activation Lotus balance portion.Transistion metal compound can be neutral (such as in pre-catalyst), or the band with counter ion counterionsl gegenions Electric species (such as in the catalyst system of activation).

As used herein, complex compound is also frequently referred to as catalyst precarsor, pre-catalyst, catalyst, catalyst compounds, mistake Cross metallic compound or transition metal complex.These words are used interchangeably.Activator and co-catalyst are also used interchangeably.

Scavenger is usual addition to promote the compound of polymerization by removing impurity.Some scavengers can also act as Activator and activator promotor can be referred to as.Some scavengers can also act as chain-transferring agent.It is not that scavenger helps activation Agent can also be used in combination with activator to form active catalyst.In some embodiments, activator promotor can be with transition Metallic compound is pre-mixed to form alkylated transistion metal compound.

" alkene (olefin) " (being alternatively referred to as " alkene (alkene) ") be have at least one double bond carbon and Straight chain, side chain or the cyclic compound of hydrogen.For the purpose of this specification and appended claims, when polymer or copolymer When being referred to as including alkene, the alkene being present in such polymer or copolymer is the polymerized form of alkene.For example, when title When copolymer has " ethene " content of 35 weight %-55 weight %, it can be understood as the monomeric unit in copolymer is polymerizeing Deposited derived from reaction from ethene, and based on the weight of the copolymer, the derived units with 35 weight %-55 weight % ." polymer " has two or more identical or different monomeric units." homopolymer " has same monomer unit Polymer." copolymer " is the polymer for having two or more monomeric units different from each other." terpolymer " is tool There is the polymer of three kinds of monomeric units different from each other.For represent monomeric unit " different " the expressions monomeric units that This is with differing at least one atom or isomerism different.Therefore, as used herein, the definition of copolymer includes terpolymer Deng." ethene polymers " or " ethylene copolymer " is the polymer or copolymer for including at least 50 moles % ethylene-derived units, " acrylic polymers " or " propylene copolymer " is the polymer or copolymer for including at least 50 moles % propylene derived units, etc. Deng.

For purposes of the invention, ethene is considered as alpha-olefin.

As used herein, Mn is number-average molecular weight, and Mw is weight average molecular weight, and Mz is z average molecular weights, and weight % is weight Percentage, a mole % are mole percents.Molecular weight distribution (MWD) (also referred to as polydispersity) is defined as Mw divided by Mn.Unless It is otherwise noted, otherwise all molecular weight units (for example, Mw, Mn, Mz) are g/mol.

Unless otherwise stated, all fusing points (Tm) are DSC second meltings.

" ring carbon atom " is the carbon atom as a part for ring-type ring structure.Thus define, benzyl has 6 ring carbon originals Son, and p-methylstyrene also have 6 ring carbon atoms.

Term " aryl " or " aromatic yl group " refer to the aromatic ring of six carbon and its substituted variation, include but not limited to benzene Base, 2- methylphenyls, xylyl, the bromo- xylyls of 4-.Similarly, heteroaryl refers to wherein ring carbon atom (or 2- or 3- Ring carbon atom) by the aryl of hetero atom (preferably N, O or S) substitution.

Term " annular atom " refers to the atom of the part as ring-type ring structure.Thus define, benzyl has 6 ring originals Son, and tetrahydrofuran have 5 annular atoms.

Term " heterocycle " and " ring of heterocycle " are used interchangeably.

Heterocycle is that have heteroatomic ring, the hetero atom substituted with the hydrogen wherein on annular atom by hetero atom in ring structure Substituted ring is opposite.For example, tetrahydrofuran and pyridine are heterocycles, N, N- dimethylaminos benzene is not heterocycle, but the virtue substituted Base.

As used herein, term " aromatics " refers to there is alternate singly-bound and 6 yuan of carbocyclic rings of double bond, such as benzene and relevant Derivative.In addition, term used herein also refers to the property and structure (be almost plane) similar with aromatic compounds Heterocycle and substitution heterocycle.The example of such molecule include pyridine, carbazole, imidazoles,Azoles and thiazole.

Term " continuous " refers to the system run in the case of no interrupting or stopping.For example, production polymer Continuation method will be the method that reactant is introduced continuously into one or more reactors and continuously extracts polymer product out.

Polymerisation in solution refers to that wherein polymer is dissolved in liquid polymerizaton medium (such as atent solvent or monomer are (a kind of or more Kind) or its blend) in polymerization.Polymerisation in solution is typically homogeneous.Homogeneous polymerization is wherein polymer product dissolving Polymerization in polymerisation medium.Such system is preferably haze-free, such as J.Vladimir Oliveira, C.Dariva and J.C.Pinto, Ind.Eng, Chem.Res., 2000, volume 29, described in page 4627.

Polymerisation in bulk refers to monomer to be polymerized and/or comonomer wherein is used as solvent or diluent, using seldom Or without using atent solvent as solvent or the polymerization of diluent.The atent solvent of sub-fraction can be used as catalyst and clear Except the carrier of agent.Bulk polymerization system contains the atent solvent or diluent less than 25 weight %, preferably smaller than 10 weight %, excellent Choosing is less than 1 weight %, preferably 0 weight %.

Unless otherwise stated, " catalyst activity " is that use includes W mmol transition gold in period when T is small The polymerization catalyst of category produces measuring for how many grams polymer (P)；And it can be represented by the following formula：P/(T x W).

The present invention provides the new catalyst compounds of the 4th race's pyridinylamino, it is characterised in that both following：(1) Metallized carbon anion donor groups and pyrrole are contained in 7 yuan of chelate rings containing amino donor groups and pyridine donor groups, and (2) 5 yuan of chelate rings of pyridine donor groups.These catalyst can be used for the polyolefin of production wide scope, including polyethylene, ethene-α-alkene Hydrocarbon copolymer, isotactic polypropylene (iPP), poly alpha olefin (PAO), ethylene propylene copolymer rubber (EPR) and ethylene, propylene Diolefinic monomer copolymer (EPDM).

The invention further relates to the method for olefin polymerization, including make alkene with comprising activator and one or more by formula (I), (II) or (III) represent compound catalyst system contact：

Wherein：

M is the race of the 3rd, 4 or 5 metal；

R¹Alkyl (such as halocarbyl, the halocarbyl of substitution, silicyl are carbon-based) and polar group selected from alkyl, substitution Group；

Each R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³And R¹⁴, independently selected from hydrogen, halogen, alkyl, the hydrocarbon substituted Base (such as halocarbyl, the halocarbyl of substitution, silicyl are carbon-based) and polar group, and any adjacent R group can The ring of substituted or unsubstituted carbocyclic ring or heterocycle is formed with engagement；

R³And R⁴It can engage to form ring, and R¹⁰And R¹¹It can engage to form ring (preferably, engagement R³R⁴Group for- CH₂CH₂- five-membered ring, or engagement R¹⁰R¹¹Group is-CH₂CH₂CH₂- hexatomic ring)；

X and L groups can be engaged covalently；

N is 1,2 or 3；

Y is 0,1 or 2；

Wherein n+y is not more than 4.

In preferred embodiments, alkene includes ethene and/or propylene.

Catalyst complex

In the first aspect of the present invention, there is provided the transition metal complex represented by formula (I), (II) or (III) is (optionally For olefinic polymerization)：

Wherein：

M is the race of the 3rd, 4 or 5 metal, preferably Hf, Zr, Ti, Sc, Y, V, Na or Ta, preferably Hf, Zr or Ti；

X is anion leaving group, and wherein X group can be identical or different, and any two X group can connect shape Into dianion leaving group；

L is neutral Lewis base, and any two L groups can engage to form bidentate lewis base；

X and L groups can be engaged covalently；

N is 1,2 or 3；

Y is 0,1 or 2；

Wherein n+y is not more than 4.

In upper formula (I), (II) and (III), dotted line represents optional key, and solid line represents key.J groups are containing at least 6 The aromatic group of a carbon, it is combined in a manner of forming 5 yuan or 6 yuan or 7 yuan of chelate rings with metal center.Q groups are and CNC pieces Section engagement forms the carbon containing fragment of aromatic heterocycle (such as pyridine, imidazoles, thiocarbamoyl imidazole).

In any embodiment of invention as described herein, M can be the group 4 transition metal of the 3rd, 4 or 5, preferably Ti, Zr or Hf, most preferably Zr or Hf.

In any embodiment of invention as described herein, R¹Selected from alkyl (such as alkyl and aryl), substitution Alkyl (such as heteroaryl) and silicyl, preferably R¹Selected from methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, Nonyl, decyl, phenyl and its isomers.

In any embodiment of invention as described herein, R¹Alkyl, the alkyl of substitution, halo carbon can be selected from Base, substitution halocarbyl, silicyl is carbon-based and polar group, it is preferable that R¹Selected from differently being substituted by 0-5 substituent Phenyl, the substituent includes F, Cl, Br, I, CF₃, NO2, alkoxy, dialkyl amido, aryl, and there is 1-10 carbon Alkyl, such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl and its isomers.Some tools Body example will include R¹Selected from including following group：2- aminomethyl phenyls, 2- isopropyl phenyls, 2- ethylphenyls, 2,6- dimethyl Phenyl,Base, 2,6- diethyl phenyls, 2,6- diisopropyl phenyls and 2,4,6- triisopropyl phenyl.

In any embodiment of invention as described herein, each R²And R³Independently selected from hydrogen, halogen, alkyl, take The alkyl (such as halocarbyl, the halocarbyl of substitution, silicyl are carbon-based) and polar group in generation, and R²And R³It can connect Conjunction forms ring.

In any embodiment of invention as described herein, each R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³With R¹⁴Independently selected from hydrogen, halogen, alkyl, the alkyl (such as halocarbyl, the halocarbyl of substitution, silicyl are carbon-based) substituted And polar group, and any adjacent R group can engage to form substituted or unsubstituted carbocyclic ring or heterocycle Ring；R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³And R¹⁴Preferred group include hydrogen, fluorine-based, chloro, methyl, ethyl, third Base, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl and its isomers.

In any embodiment of invention as described herein, Q is-(TT)-or-(TTT)-, wherein each T is substitution Or unsubstituted alkyl the 14th, 15 or 16 race's elements so that it forms 5 yuan or 6 circle heterocycles together with "-C-N=C- " fragment, Preferable Q groups include-C (H) C (H) C (H)-,-C (H) N (Me)-,-C (H) N (Et)-,-C (H) O- and-C (H) S-.

In any embodiment of invention as described herein, J can be by carbanion donor and metal center The aromatic group containing 4-40 carbon atom of coordination, preferable J groups include C₆H₄、C₁₀H₆、C₁₂H₇N and C₁₄H₈。

In any embodiment of invention as described herein, preferably X is selected from halogen, alkyl, aryl, alkoxy, ammonia Base, hydride ion (hydrido), phenoxy group, hydroxyl, alkyl azochlorosulfonate, carboxylate radical, silicyl, pi-allyl, alkenyl and alkynes Base, preferably methyl, chloro, trifluoromethanesulfonic acid root, dimethylamino and diethylamino.The selection of leaving group depends on being used for The synthetic route of complex compound is obtained, and the activation method to adapt to subsequent in polymerization can be changed by other reaction. Non-coordinating anion such as n,N-Dimethylaniline is used for example, working asFour (pentafluorophenyl group) borates or three (pentafluorophenyl groups) During borine, preferable X is alkyl.In another embodiment, two X groups can connect to form dianion leaving group Group, such as oxalate.

In any embodiment of invention as described herein, preferably L be selected from ether, thioether, amine, nitrile, imines, pyridine and Phosphine, preferably ether, preferably Et₂O, dimethylamine, diethylamine, tetrahydrofuran and thiophane.

In any embodiment of invention as described herein, n is 1,2 or 3, y are 0,1 or 2, and wherein n+y is not more than 4, preferably n are 1 or 2, and y is 0 or 1, and n+y is 2.Or n is that 2, y is 0, and n+y is 2.

In any embodiment of invention as described herein, M is Sc, Y, Ti, Zr, Hf, V, Nb or Ta；And R²And R³ Hydrogen, C can independently be₁-C₂₀Alkyl, preferably methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, the last of the ten Heavenly stems Base, undecyl, dodecyl or its isomers), or C₅-C₄₀Aryl (preferably C₆-C₂₀Aryl, preferably phenyl or substituted benzene Base or its isomers, preferably phenyl, 2- isopropyl phenyls or 2- tert-butyl-phenyls).

In any embodiment of invention as described herein, R¹It is former containing 1-30 carbon atom, preferably 2-20 carbon Son.

In any embodiment of invention as described herein, M can be Ti, Zr or Hf, and R¹It is 2,6- dioxanes The complex compound of base phenyl and Zr or Hf bases is particularly preferred.

In any embodiment of invention as described herein, M is Zr or Hf, R²And R³The two is all hydrogen, and J is Aromatic carbocyclic containing 6-14 carbon.

In any embodiment of invention as described herein, M is group-4 metal, R²For hydrogen, R³And R⁴Engagement forms 5 Yuan of rings, wherein R³R⁴Unit is-CH₂CH₂-。

In any embodiment of invention as described herein, M is group-4 metal, R²For hydrogen, R³And R⁴Engagement forms 6 Yuan of rings, wherein R³R⁴Unit is-CH₂CH₂CH₂-。

In any embodiment of invention as described herein, M is group-4 metal, R²For hydrogen, R¹⁰And R¹¹Engagement is formed 6 yuan of rings, wherein R¹⁰R¹¹Unit is-CH₂CH₂CH₂-。

In preferred embodiments, transition metal complex is represented by upper formula (III), y 0, and M is the 4th race gold Belong to, preferably Zr or Hf, preferably Hf.

In preferred embodiments, R²For H and R³To include the base of 1-100 (preferably 6-40, preferably 6-30) a carbon Group, M is group-4 metal (preferably Zr or Hf, preferably Hf), alternatively R²With R³It is identical, and preferably hydrogen or methyl.

In another aspect of the present invention, there is provided for synthesizing the various methods of complex compound as described herein.

Ligand synthesizes

Being used to prepare the CNN ligands of complex compound as described herein can make according to general scheme given below It is standby.The pyridine substituted with aromatic group (Int-1) is known in document, and some can be obtained from commercial source (for example, 2- phenylpyridines from Sigma-Aldrich).Int-1 can use highly basic, such as 2:1 butyl lithium:N, N- dimethylamino Ethanol ortho position deprotonation (for example, with reference to：Journal of Organic Chemistry, volume 2003,68, the 2028th Page).This lithiumation material can be reacted with electrophilic Br sources such as tetrabromomethane or 1,2- Bromofume, obtain Int-2.Int-2 Pd catalyst such as Pd (PPh can be used₃)₄It is coupled with borate Int-3.The borate for being shown as Int-3 formulas can be as Prepared described in US2014/0221587, US2014/0316089 and US2015/0141601.The CNN prepared by this method matches somebody with somebody Body can by crystallization, chromatography or by Separation of Neutral CNN ligands with acid reaction formed their salt, then by with alkali Reaction carries out washing and deprotonation to purify.

Wherein R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰As described above, and HJ is to match somebody with somebody containing 4-40 the non-of carbon atom Position aromatic group, it can be with deprotonation, to form the group by carbanion coordinating to metal center.

CNN ligands can use various known methods to coordinate with 3-5 group 4 transition metals.A kind of usually useful method It is as follows.This includes the directly reaction of neutrality CNN ligands and alkalescence organometallic reagent M (X) n+2, and wherein X is can be with Property CNN ligands two proton reactions with formed gained transition metal complex and eliminate two equivalent XH anion leaving group Group.Common reactive X group includes hydrogen-based, alkyl and amino.It is for these some transition metal reagents converted ZrBn₄、HfBn₄、TiBn₄、Zr(NMe₂)₄、Hf(NMe₂)₄、Hf(NMe₂)₂C₁₂(1,2- dimethoxy-ethanes), ZrBn₂C_l2 (OEt₂)、HfBnC₁₂(OEt₂)x、TaMe₃C_l2And TaMe₂C_l3.In the transition metal reagent of the X group comprising mixing, reaction Property relatively low anion X group, be usually chloro, will be retained on transition metal, and the higher X group of reactivity will be used as it Corresponding conjugate acid XH is eliminated.

Wherein M, X, n, L, y, R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³And R¹⁴As described above.

CNN ligands and the reaction of M (X) n+2 can result in intermediate complex first, have and pass through ammonia nitrogen and neutrality The two tooth ligands that lewis base is combined with M (X) n+1 fragments.The example of this bidentate species is shown below, i.e., it is " middle Bidentate complex compound ".The middle species can separate, and can even be used as catalytic component together with common activator, this It is because it is converted into the CNN complex compounds of the invention for being characterized in that three tooth CNN ligands in further reaction.Among bidentate Body can by CNN ligands under relatively mild condition (i.e. lower temperature) with transition metal amide reagent such as M (ammonia Base) 4 (wherein M is group-4 metal) reaction and formed.Two tooth intermediates can be by heating or making it to eliminate HX (wherein hydrogen sources From J groups) other methods be converted into CNN complex compounds (I).

Wherein HJ, J, Q, M, X, n, L, y, R¹、R²、R³、R⁴、R⁵、R⁶And R⁷As described above.

The selective route of CNN complex compounds includes the reaction of the alkali of neutrality CNN ligands and the 1st or 2 races to form amino Salt, such as Li [CNN ligands].Anion CNN species can then reacted with shape with transition metal halide M (halogen) n+2 Into the bidentate complex compound of general formula [bidentate CNN ligands] M (halogen) n+1.It is expected that the species and alkylating reagent (such as MeMgBr or MeLi reaction) will form three tooth CNN complex compounds [CNN] M (alkyl) n, while eliminate lithium halide and alkyl-H.It is this selective Route example will be make the butyl lithium of CNN ligands and monovalent reaction generation amino lithium species.Then the lithium salts can be made With HfCl₄React to form formula [bidentate CNN ligands] HfCl₃Species, while lose LiCl.Methylating the species with MeLi will It is initially formed [bidentate CNN ligands] HfMe₃, it is contemplated that methanogenesis three tooth complex compound [CNN] HfMe will be eliminated₂。

Activator

, can be by the way that they be combined with activator in a manner of known in the literature is any after complex compound has synthesized Catalyst system is formed, including is used for slurry or gas-phase polymerization by the way that them will be loaded.Catalyst system can also be added to molten Liquid polymerize or polymerisation in bulk in produce (in monomer) or wherein.Catalyst system generally comprise complex compound as described above and Activator such as aikyiaiurnirsoxan beta or non-coordinating anion.It can be activated using aluminoxanes solution, the aluminoxanes solution includes Methylaluminoxane (is referred to as MAO), and (referred to herein as MMAO, it includes some senior alkyls to improve by modified MAO Solubility).Especially, useful MAO can be bought from Albemarle, usually with the toluene solution of 10 weight %.For this hair Bright catalyst system is preferably using (such as methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, different selected from aikyiaiurnirsoxan beta Butyla-luminoxane etc.) activator.

When using aikyiaiurnirsoxan beta or modified alumoxane, the molar ratio of complex compound and activator is about 1:3000-10:1；For choosing Select ground 1:2000-10:1；Alternatively 1:1000-10:1；Alternatively 1:500-1:1；Alternatively 1:300-1:1；For choosing Select ground 1:200-1:1；Alternatively 1:100-1:1；Alternatively 1:50-1:1；Alternatively 1:10-1:1.When activator is During aikyiaiurnirsoxan beta (being modified or unmodified), some embodiments are selected relative to catalyst precarsor (each metal catalytic site) The maximum of the activator of 5000 times of molar excess.Preferable minimum activator and complex compound ratio are 1:1 molar ratio.

Can also use described in EP 277 003 and EP 277 004, also referred to as NCA non-coordinating anion come into Row activation.NCA can be added in the form of ion pair (using such as [DMAH]+[NCA] -), wherein N, accelerine (DMAH) the alkaline leaving group on cation and transition metal complex react to be formed transition metal complex cation and [NCA]-.Cation in precursor can be alternatively trityl.Alternatively, transition metal complex can be with neutrality NCA precursors such as B (C₆F₅)₃(it captures anionic group to form activation species from complex compound) reaction.Useful activator Including N, accelerineFour (pentafluorophenyl group) borate (i.e. [PhNMe₂H]B(C₆F₅)₄) and N, accelerine Four (seven fluoronaphthalene bases) borates, wherein Ph is phenyl, and Me is methyl.

The preferable activator that may be additionally used for this paper is included in US 7,247,687 in the 50th row of the 169th column to the 174th The 43rd row of column, particularly the 24th row of the 172nd column to those described in the 53rd row of the 173rd column.

Non-coordinating anion (NCA) is defined as referring to does not match somebody with somebody with catalyst metals cation coordination or with metal cation Position, but the anion of only weak coordination.Term NCA is also defined as including containing acid cation group and non-coordinating anion Activator of the multicomponent containing NCA, such as n,N-DimethylanilineFour (pentafluorophenyl group) borates.Term NCA is also defined as Including neutral lewis acid, such as three (pentafluorophenyl group) boron, its can by capture anionic group and with catalyst reaction with Form activation species.NCA is coordinated enough weakly so that neutral Lewis base, such as olefinic or acetylene series unsaturated monomer, can be by it Cemented out from catalyst center.Any metal that can form compatible weak co-ordination complex or metalloid can be used for or Included in non-coordinating anion.Suitable metal includes but not limited to aluminium, gold and platinum.Suitable metalloid includes but not limited to Boron, aluminium, phosphorus and silicon.Stoichiometric activators can be neutral or ion.The agent of term ion activation and stoichiometry ion Activator is interchangeable.Similarly, term neutral stoichiometric activator and Lewis acid activation agent are interchangeable. Term non-coordinating anion includes neutral stoichiometric activator, Ionic stoichiometric activator, ion activation agent and Louis Acid activators.

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

(Z)d⁺(A^d-) (1)

Wherein Z is (L-H) or reducible lewis acid；L is neutral Lewis base；H is hydrogen, and (L-H)⁺It is Blang Si Taide acid；A^d-It is the non-coordinating anion with electric charge d-, d is the integer of 1-3.

When Z be (L-H) so that cationic components are (L-H) d+ when, the cationic components can include Bronsted Acid, such as such as alkyl or aryl of the part from catalyst precarsor can be made to protonate to obtain cationic transition metal species Protonated Lewis base, or activating cations (L-H) d+ are Bronsted acid, and proton, production can be provided to catalyst precarsor Raw transition-metal cation, including ammonium, oxygenPhosphorusMonosilaneAnd its mixture, or methylamine, aniline, dimethylamine, two Ethamine, methylphenylamine, diphenylamines, trimethylamine, triethylamine, n,N-Dimethylaniline, methyldiphenylamine, pyridine, to bromo- N, N- Dimethylaniline, the ammonium to nitro-n,N-Dimethylaniline, from triethyl phosphine, triphenylphosphine, diphenylphosphine phosphorusCome From ether (such as dimethyl ether, Anaesthetie Ether, tetrahydrofuran, twoAlkane) oxygenFrom thioether (such as such as diethyl thioether And thiophane) sulfonium, and its mixture.

When Z is can to reduce lewis acid, it can be expressed from the next：(Ar₃C⁺), wherein Ar is for aryl or by hetero atom Or the aryl of C1-C40 alkyl substitution, reducible lewis acid can be expressed from the next：(Ph₃C⁺), wherein Ph be phenyl or The phenyl substituted by hetero atom and/or C1-C40 alkyl.In one embodiment, reducible lewis acid is triphenylcarbenium

The embodiment of anionic group Ad- includes those with formula [Mk+Qn] d-, and wherein k is 1,2 or 3；N is 1, 2nd, 3,4,5 or 6, or 3,4,5 or 6；N-k=d；M is the element selected from the 13rd race of the periodic table of elements, or boron or aluminium, and Q is independently It is hydrogen-based, bridging or non-bridged dialkyl amido, halogen, alkoxy, aryloxy group, alkyl, the Q has at most 20 carbon originals Son, condition is that Q is halogen when not more than once occurring, and two Q groups can form ring structure.Each Q can be tool There is the fluorination alkyl of 1-20 carbon atom, either each Q is fluoro aryl or each Q is five fluorenyl aryl.Suitable Ad- The example of component is additionally included in U.S. Patent number 5, two boron compounds disclosed in 447,895, it is fully incorporated this by quoting Text.

In the embodiment of any of the NCA that above-mentioned formula 1 represents, anionic group Ad- is by formula [M*k*+Q*n*] D*- represents that 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* Independently selected from hydrogen-based, bridging or non-bridged dialkyl amido, halogen, alkoxy, aryloxy group, alkyl, the Q* has extremely More 20 carbon atoms, condition are that Q* is halogen when occurring for not more than 1 time.

The invention further relates to the method for olefin polymerization, it includes making alkene (such as propylene) and catalyst network as described above Compound and the NCA activators represented by formula (2) contact：

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

Wherein R is single anion ligand；M** is the 13rd race's metal or metalloid；ArNHal is the nitrogenous aromatic ring of halogenation, Polycyclic aromatic ring or aromatic ring set (assembly), two of which or more ring (or fused ring system) be directly engaged with each other or Common engagement；And n is 0,1,2 or 3.In general, the NCA of the anion comprising formula 2 also includes suitable cation, it is substantially Ionic catalyst complex compound with being formed by transistion metal compound is not interfere with each other, or the cation is Z as described above_d ⁺。

In any embodiment of the NCA comprising the anion represented by above-mentioned formula 2, R is selected from C1-C30 alkyl. In one embodiment, C1-C30 alkyl can be by following substitution：One or more C1-C20 alkyl, halogen, alkyl substitution Organic quasi-metal, dialkyl amido, alkoxy, aryloxy group, alkyl sulfenyl (alkysulfido), artyl sulfo (arylsulfido), alkyl phosphorus base (alkylphosphido), aryl phosphorus base (arylphosphide) or other anion take Dai Ji；It is fluorine-based；Large volume alkoxy, wherein large volume refer to C4-C20 alkyl；--SR^a,--NR^a ₂With -- PR^a ₂, wherein each R^aIt independently is the monovalence C4-C20 alkyl or tool of the molecular volume of the molecular volume comprising more than or equal to isopropyl substituents There is the organic quasi-metal of the C4-C20 alkyl substitution of the molecular volume more than or equal to isopropyl substituents volume of molecular volume.

In any embodiments of the NCA comprising the anion represented by above-mentioned formula 2, NCA, which is also included, to be contained under Reducible lewis acidic cation that formula represents：(Ar₃C+), wherein Ar is for aryl or by hetero atom and/or C1-C40 hydrocarbon The aryl of base substitution, or the reducible lewis acid being expressed from the next：(Ph₃C+), wherein Ph is phenyl or by one or more A hetero atom, and/or the phenyl of C1-C40 alkyl substitution.

In any embodiments of the NCA comprising the anion represented by above-mentioned formula 2, NCA can also be included by formula (L-H) cation that d+ is represented, wherein L is neutral Lewis base；H is hydrogen；(L-H) it is Bronsted acid；And d is 1,2 Or 3, or (L-H) d+ is selected from ammonium, oxygenPhosphorusMonosilaneAnd its Bronsted acid of mixture.

Other examples of useful activator are included in US 7,297,653 and US 7, those disclosed in 799,879, its It is fully incorporated herein by quoting.

In one embodiment, the activator available for this paper includes the cation oxidant and non-represented by formula (3) The salt of coordinating compatible anion：

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

Wherein OX^e+It is the cation oxidant with electric charge e+；E is 1,2 or 3；D is 1,2 or 3；And A^d-It is with d- The non-coordinating anion (as further described above) of electric charge.The example of cation oxidant includes：Ferrocene (ferrocenium), ferrocene, the Ag of alkyl substitution⁺Or Pb⁺²。A^d-Suitable embodiment include four (pentafluorophenyl group) boric acid Root.

Include available for the activator in the catalyst system of this paper:Trimethyl ammonium four (perfluoronapthyl) borate, N, N- DimethylanilineFour (perfluoronapthyl) borates, N, N- diethylanilinesFour (perfluoronapthyl) borates, triphenylcarbeniumFour (perfluoronapthyl) borates, trimethyl ammonium four (perfluorinated biphenyl) borate, n,N-DimethylanilineFour (perfluor connection Phenyl) borate, triphenylcarbeniumFour (perfluorinated biphenyl) borates, and US 7, the type disclosed in 297,653, it is logical Reference is crossed to be fully incorporated herein.

Suitable activator further includes：

N,N-DimethylanilineFour (perfluoronapthyl) borates, n,N-DimethylanilineFour (perfluorinated biphenyl) boron Hydrochlorate, n,N-DimethylanilineFour (double (trifluoromethyl) phenyl of 3,5-) borates, triphenylcarbeniumFour (perfluoronapthyl) boron Hydrochlorate, triphenylcarbeniumFour (perfluorinated biphenyl) borates, triphenylcarbeniumFour (double (trifluoromethyl) phenyl of 3,5-) boric acid Salt, triphenylcarbeniumFour (perfluorophenyl) borates, [Ph3C+] [B (C6F5) 4-], [Me3NH+] [B (C6F5) 4-]；1-(4- (three (pentafluorophenyl group) borates) -2,3,5,6- tetrafluoros phenyl) pyrrolidinesWith four (pentafluorophenyl group) borates, 4 (three (five fluorine Phenyl) borate) -2,3,5,6- ptfe pyridines.

In one embodiment, activator includes triaryl carbon(such as triphenylcarbenium tetraphenyl borate salts, triphen Base carbonFour (pentafluorophenyl group) borates, triphenylcarbeniumFour (2,3,4,6- tetrafluoros phenyl) borates, triphenylcarbeniumFour (perfluoronapthyl) borate, triphenylcarbeniumFour (perfluorinated biphenyl) borates, triphenylcarbeniumFour (double (the fluoroforms of 3,5- Base) phenyl) borate).

In one embodiment, two kinds of NCA activators, and the first NCA activators and can be used in polymerization The molar ratio of two NCA activators can be arbitrary proportion.In one embodiment, the first NCA activators and the 2nd NCA are activated The molar ratio of agent is 0.01:1-10,000:1, or 0.1:1-1000:1 or 1:1-100:1.

In one embodiment of the present invention, the ratio of NCA activators and catalyst is 1:1 molar ratio, or 0.1: 1-100:1, or 0.5:1-200:1, or 1:1-500:1, or 1:1-1000:1.In one embodiment, NCA is activated The ratio of agent and catalyst is 0.5:1-10:1 or 1:1-5:1.

In one embodiment, catalyst compounds can merge (see, for example, US with the combination of aikyiaiurnirsoxan beta and NCA 5,153,157, US 5,453,410, EP 0 573 120, WO 94/07928 and WO 95/14044, it is discussed using alumina The combination of alkane and Ionizing activators, all these to be incorporated herein by reference).

In a preferred embodiment of the invention, when using NCA (such as ion or neutral stoichiometric activator), network The molar ratio of compound and activator is usually 1:10-1:1；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, activator promotor or chain-transferring agent, such as the 1st, 2 or 13 can also be used in the catalyst system of this paper Race's organometallic species (for example, alkyl aluminum compound such as tri-n-octylaluminium).The molar ratio of complex compound and activator promotor 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-transferring agent

" chain-transferring agent " is in the course of the polymerization process can be between coordination polymerization catalysts and the metal center of chain-transferring agent Carry out any reagent that alkyl and/or polymeric groups exchange.Chain-transferring agent can be any desired chemical compound, such as Those compounds disclosed in WO 2007/130306.Preferably, chain-transferring agent is selected from the 2nd, 12 or 13 race's alkyl or aryls Compound；Optimizing alkyl zinc or aryl zinc, alkyl magnesium or aryl magnesium or alkyl aluminum or aryl aluminium；Alkyl is C1- preferably wherein C30 alkyl, alternatively C2-C20 alkyl, alternatively C3-C12 alkyl, is generally selected from methyl, ethyl, propyl group, butyl, different Butyl, the tert-butyl group, amyl group, hexyl, cyclohexyl, phenyl, octyl group, nonyl, decyl, undecyl and dodecyl；And wherein Diethyl zinc is particularly preferred.

In particularly useful embodiment, the present invention relates to include activator as described herein, catalyst complex With the catalyst system of chain-transferring agent, wherein the chain-transferring agent is selected from the 2nd, 12 or 13 race's alkyl or aryl compounds.

In particularly useful embodiment, the chain-transferring agent is selected from dialkyl zinc compounds, wherein the alkyl is only On the spot it is selected from methyl, ethyl, propyl group, butyl, isobutyl group, the tert-butyl group, amyl group, hexyl, cyclohexyl and phenyl.

In particularly useful embodiment, the chain-transferring agent is selected from trialkyl aluminium compound, wherein the alkyl is only On the spot it is selected from methyl, ethyl, propyl group, butyl, isobutyl group, the tert-butyl group, amyl group, hexyl, cyclohexyl and phenyl.

Relative to catalytic component, useful chain-transferring agent usually with 10 or 20 or 50 or 100 equivalents to 600 or 700 or 800 or 1000 equivalents exist.Alternatively, chain-transferring agent (" CTA ") is using catalyst complex and CTA molar ratios as about 1: 3000-10:1；Alternatively 1:2000-10:1；Alternatively 1:1000-10:1；Alternatively 1:500-1:1；Alternatively 1:300-1:1；Alternatively 1:200-1:1；Alternatively 1:100-1:1；Alternatively 1:50-1:1；Alternatively 1:10- 1:1 exists.

Useful chain-transferring agent includes diethyl zinc, tri-n-octylaluminium, trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three N-hexyl aluminium, diethyl aluminum chloride, dibutyl zinc, diη-propyl zinc, di-n-hexyl zinc, two n-pentyl zinc, two positive decyl zinc, two Dodecyl zinc, two n-tetradecane base zinc, two n-hexadecyl zinc, two n-octadecane base zinc, diphenyl zinc, two isobutyls of hydrogenation Base aluminium, diethyl aluminium hydride, hydrogenation di-n-octyl aluminium, dibutylmagnesium, magnesium ethide, dihexyl magnesium and boron triethyl.

Carrier

In some embodiments, this can be loaded by any method of the other coordination catalyst systems of payload Complex compound described in text (in the case where being with or without activator).The catalyst so prepared can be used for low with heterogeneous procedures Poly or poly conjunction alkene.Catalyst precarsor, activator, activator promotor (if desired), suitable solvent and carrier can be with any Serially or simultaneously add.In general, complex compound and activator can merge to form solution in a solvent.Then carrier is added, and Stir mixture 1 minute -10 it is small when.Total solution volume can be more than the pore volume of carrier, but some embodiments will be total molten Liquid product is limited in less than forming gel or the volume (hole body of about 90%-400%, preferably from about 100-200% needed for slurry Product).After stirring, usually at ambient temperature and interior when 10-16 is small residual solvent is removed in vacuum.But more or less Time and higher or lower temperature be feasible.

The complex compound can also load in the case of no activator；It that case, activator (and is helped into activation Agent, if desired) be added in the liquid phase of polymerization.In addition, two or more different complex compounds can be placed On identical carrier.Equally, two or more activators or activator and activator promotor can be placed on identical load On body.

Suitable solid particulate carrier is usually made of polymer or refractory oxide material, and every kind of material is preferably porous 's.Any carrier material of the preferred average particle size more than 10 μm is suitable for the present invention.Various embodiments select porous carrier material Material, such as talcum, inorganic oxide, butter, such as magnesium chloride and resinous support material, such as polystyrene polyolefin Or polymer compound or any other organic support material etc..Some embodiments select inorganic oxide material as carrier Material, including the 2nd race, -3 races, -4 races, -5 races, -13 races or -14 family metal oxides or quasi-metal oxide.Some are implemented Scheme Choice catalyst carrier material includes silica, aluminium oxide, silica-alumina and its mixture.It is other inorganic Oxide can be used alone or is applied in combination with silica, aluminium oxide or silica-alumina.These be magnesia, Titanium oxide, zirconium oxide etc..Such as montmorillonite of lewis acidity material and similar clay are also used as carrier.In such case Under, carrier can be doubled optionally as activator component, it is also possible, however, to use other activator.

Carrier material can be pre-processed by any amount of method.For example, inorganic oxide can be calcined, deshydroxy is used Base reagent such as alkyl aluminum etc. is chemically treated, or both more than progress.

As described above, according to the present invention, polymer support also will be suitable, see, for example, WO95/15815 and US 5, Description in 427,991.Disclosed method can be together with the catalyst complex, activator or catalyst system of the present invention Use, adsorbed with absorption or by them on polymer support, particularly if when being made of porous particle, or can pass through It is bonded to polymer chain or the chemical functional groups bonding in polymer chain.

Useful carrier usually has 10-700m²The surface area of/g, the pore volume of 0.1-4.0cc/g and 10-500 μm Particle mean size.Some embodiments select 50-500m²The surface area of/g, the pore volume of 0.5-3.5cc/g or 20-200 μm it is flat Equal granularity.Other embodiments select 100-400m²The surface area of/g, the pore volume of 0.8-3.0cc/g and 30-100 μm it is flat Equal granularity.Useful carrier usually has 10-1000 angstroms, alternatively 50-500 angstroms or 75-350 angstroms of aperture.

Catalyst complex as described herein is usually with the load capacity of every gram of micromolar complex compound of solid carrier 10-100 It is deposited on carrier；Alternatively every gram of micromolar complex compound of solid carrier 20-80；Or every gram of carrier 40-60 is micromolar Complex compound.But greater or lesser value can be used, condition is that the total amount of solid complex is no more than the pore volume of carrier.

Polymerization

The catalyst complex of the present invention can be used for polymerizeing conventionally known (such as molten available for experience polymerization catalyzed by metallocene Liquid, slurry, gas phase and high pressure polymerisation) unsaturated monomer.Usually make the one or more in complex compound as described herein, it is a kind of Or a variety of activators and one or more monomers are contacted to produce polymer.In certain embodiments, complex compound can be born Carry, and therefore that carried out in single, serial or parallel connection reactor known fixed bed, moving bed, fluid bed, slurry, To be particularly useful in solution or body operator scheme.

The reactor of one or more serial or parallel connections can be used in the present invention.Complex compound, activator and (work as needs When) activator promotor can be used as solution or slurry be delivered to reactor respectively, activated online before immediately reactor, or in advance Activating and conduct activated solution or slurry are pumped to reactor.It is polymerize in single reactor operation, wherein by monomer, being total to Polycondensation monomer, catalyst/activator/activator promotor, optional scavenger and optional modifying agent are continuously added in single-reactor, Or in tandem reactor operation, wherein said components are added to each in two or more reactors being connected in series In.Catalytic component can be added in the first reactor of series connection.Catalytic component can also be added to two reactions In device, one of which component is added in first reactor, and another component is added in another reactor.A kind of excellent In the embodiment of choosing, the activated complex in the reactor in the presence of alkene.

In particularly preferred embodiments, polymerization is continuation method.

Polymerization used herein generally includes to make one or more olefinic monomers and complex compound as described herein (and to appoint The activator of choosing) contact.For purposes of the invention, alkene is defined as including polyene (such as alkadienes) and only had The alkene of one double bond.Polymerization can be homogeneous (polymerisation in solution or polymerisation in bulk) or heterogeneous (slurry-in liquid diluent In, or gas phase-in diluent for gases).In the case of heterogeneous slurry or gas-phase polymerization, complex compound and activator can be by Load.Silica can be used as the carrier of this paper.In chain-transferring agent (such as hydrogen or diethyl zinc) implementation for use in the present invention.

The polymerization of the present invention can preferably include about 30 DEG C-about 200 DEG C, preferably from about 60 DEG C-about 195 DEG C, preferably Carried out under conditions of about 75 DEG C-about 190 DEG C of temperature.This method can carry out under the pressure of 0.05Mpa-1500MPa.Excellent Select in embodiment, pressure is between 1.7Mpa-30Mpa, or in another embodiment, particularly in super critical condition Under, pressure is between 15Mpa-1500MPa.

Monomer

Monomer available for this paper includes having 2-20 carbon atom, and alternatively the alkene of 2-12 carbon atom is (preferably Ethene, propylene, butylene, amylene, hexene, heptene, octene, nonene, decene and dodecylene), and optionally also have polyenoid (such as Diene).Particularly preferred monomer includes ethene, and the mixture of C2-C10 alpha-olefins, as ethylene-propylene, polyethylene-hexene, Ethylene-octene, butene-hexene etc..

Complex compound as described herein for ethene be polymerized alone or ethene and at least one other ethylenically unsaturated monomer The polymerization of (such as C3-C20 alpha-olefins, particularly C3-C12 alpha-olefins) combination is also particularly effective.Equally, network of the invention Compound for propylene be polymerized alone or propylene and at least one other ethylenically unsaturated monomer (such as ethene or C4-C20 α-alkene Hydrocarbon, particularly C4-C20 alpha-olefins) combination polymerization be also particularly effective.The example of preferable alpha-olefin includes ethene, third Alkene, butene-1, amylene -1, hexene -1, heptene -1, octene-1, nonylene-1, decylene-1, dodecylene -1,4- methylpentenes -1, 3- methylpentenes -1,3,5,5- trimethylhexenes -1 and 5- ethyl nonylene-1s.

In some embodiments, based on monomer mixture, monomer mixture may also contain up to 10 weight %, such as 0.00001-1.0 weight %, such as 0.002-0.5 weight %, such as one or more diene of 0.003-0.2 weight %.Have The non-limiting examples of diene include cyclopentadiene, norbornadiene, bicyclopentadiene, 5- ethylidene -2- norbornene, 5- vinyl -2- norbornene, 1,4- hexadienes, 1,5- hexadienes, 1,5- heptadiene, 1,6- heptadiene, 6- methyl isophthalic acids, 6- heptan Diene, 1,7- octadienes, 7- methyl isophthalic acids, 7- octadienes, 1,9- decadinene and 9- methyl isophthalic acids, 9- decadinene.

Using in the case of causing short-chain branched alkene such as propylene, catalyst system can produce under proper condition Raw stereoregular polymer or the polymer in polymer chain with stereospecific sequence.

Scavenger

In some embodiments, when using complex compound as described herein, particularly when they are fixed on carrier, Catalyst system will additionally comprise one or more removing compounds.Refer to here, term removes compound from reaction environment Remove the compound of polar impurity.These impurity negatively affect catalyst activity and stability.In general, removing compound will be Organo-metallic compound, such as US 5,153,157；US 5,241,025；WO 91/09882；WO 94/03506；With WO 93/ The organo-metallic compound of 14132 the 13rd race, and WO 95/07941 those.Exemplary compound includes triethyl group Aluminium, boron triethyl, triisobutyl aluminium, methylaluminoxane, isobutyl aluminium alkoxide and tri-n-octylaluminium.With golden with metal or standard The large volume of category center connection or those removing compounds of C6-C20 straight-chain alkyl substituents usually make and active catalyst Unfavorable interaction minimizes.Example includes triethyl aluminum, but more preferably bulky compounds such as triisobutyl aluminium, three isoamyls Alkenyl (tri-iso-prenyl) aluminium and the alkyl-substituted aluminium compound of high amylose, such as tri-n-hexyl aluminum, tri-n-octylaluminium Or three dodecyl aluminium.When using aikyiaiurnirsoxan beta as activator, any excess exceeded needed for activation will all remove impurity, And extra removing compound can be not required.Aikyiaiurnirsoxan beta such as first can also be added with clearing amount together with other activators Base aikyiaiurnirsoxan beta, [Me₂HNPh]+[B(pfp)₄]-or B (pfp)₃(perfluorophenyl=pfp=C₆F₅)。

In preferred embodiments, two or more complex compounds and diethyl zinc in identical reactor with monomer Combination.Alternatively, by one or more complex compounds and other catalyst (such as metallocene) and chain-transferring agent (such as diethyl Base zinc and/or tri-n-octylaluminium) in identical reactor with combination of monomers.

Polymer product

Although the molecular weight of the polymer produced herein is by reactor condition, (including temperature, monomer concentration and pressure, chain are whole Only presence of agent etc.) influence, but the method for the present invention production homopolymer and copolymer products can have by GPC measure pact 1,000- about 2,000,000g/mol, alternatively about 30,000- about 600,000g/mol, or alternatively about 100,000- The Mw of about 500,000g/mol.The preferable polymer produced herein can be homopolymer or copolymer.In preferable embodiment party In case, comonomer (one or more) is with most 50mol%, preferably 0.01-40mol%, preferably 1-30mol%, preferably 5- 20mol% exists.

In some embodiments of this paper, be prepared for multimodal polyolefm composition, it includes the first polyolefin component and At least another polyolefin component, it is different from the first polyolefin component molecular weight, it is preferable that GPC trace has more than one Peak or flex point.

When for describing polymer or polymer composition, term " multimodal " refers to " multimodal molecular weight distribution ", its quilt Be understood to mean that gel permeation chromatography (GPC) trace drawn to retention time (second) with absorbance have more than one peak or Flex point." flex point " is the point of the quadratic derivative symbols change (for example, from negative to positive or vice versa) of curve.For example, comprising first compared with Low-molecular weight polymer component (such as polymer that Mw is 100,000g/mol) and the second higher molecular weight polymer component (example As Mw be 300,000g/mol polymer) polyolefin composition be considered as " bimodal " polyolefin composition.Preferably, gather The Mw of compound or polymer composition differs at least 10%, preferably at least 20%, preferably at least 50% relative to each other, preferably extremely Few 100%, preferably at least 200%.Equally, in preferred embodiments, the Mw of polymer or polymer composition relative to Differ 10%-10 each other, 000%, preferably 20%-1000%, preferably 50%-500%, preferably at least 100%-400%, preferably 200%-300%.

Unless otherwise indicated, the measurement of weight average molecular weight (Mw), number-average molecular weight (Mn) and z average molecular weight (Mz) passes through Gel permeation chromatography (GPC) measures, such as Macromolecules, volume 2001,34, the 19th phase, described in page 6812 , it is fully incorporated herein by quoting, including：Using equipped with differential refraction rate detector (DRI) (equipped with three Polymer Laboratories PLgel 10mm Mixed-B columns) high volume exclusion chromatography (SEC, Waters Alliance 2000).Instrument is operated with the flow velocity of 1.0cm3/min, the injected slurry volume of 300 μ L.Various transmission lines, column and differential Refractometer (DRI detectors), which is all positioned over, to be maintained in 145 DEG C of baking oven.

By at 160 DEG C in 1,2,4- trichloro-benzenes of the filtering containing~1000ppm Yoshinox BHTs (BHT) (TCB) when heating 0.75-1.5mg/mL polymer 2 is small in and continuously stir to prepare polymer solution.Polymer will be contained Solution example is injected into GPC, and is eluted using 1,2,4- trichloro-benzenes (TCB) of the filtering containing~1000ppm BHT. The separative efficiency of the column group, a series of narrow MWD polystyrene are corrected using a series of narrow MWD polystyrene standards Reference material reflects the expection Mw scopes of analyzed sample and the exclusion limit of column group.Using from Polymer Laboratories Peak molecular weight (Mp)~580-10 that (Amherst, MA) is obtained, 17 single polystyrene in the range of 000,000 Reference material produces calibration curve.

Before the retention volume of each polystyrene standards is determined, to each run corrected flow rate to provide flow velocity mark Remember the common peak position (being taken as just injecting peak value) of thing.When analyzing sample, flow label peak position is used for corrected flow rate. The retention volume at the peak value in DRI signals by recording each PS reference materials, and the data group is fitted to secondary multinomial Formula generates calibration curve (log (Mp) is to retention volume).Come by using the Mark-Houwink coefficients shown in following table true Settled weight northylen molecular weight.

In following experimental section, report come " the molecular weight data of the distinct methods of quick GPC " of calling oneself.If The above method has with quick GPC method to conflict, and should use the above method.

In preferred embodiments, the homopolymer and copolymer products being prepared by the method for the present invention can have about 1, 000- about 2,000,000g/mol, alternatively about 30,000- about 600,000g/mol, or alternatively about 100,000- is about 500,000g/mol Mw (it is measured by GPC) and there is multimodal, preferably bimodal, Mw/Mn.

In a preferred embodiment of the invention, ethene polymers is produced, particularly ethene polymers, it can be second The single polymer of alkene or ethene and at least one other ethylenically unsaturated monomer (such as C3-C20 alpha-olefins, particularly C3- C12 alpha-olefins) combination polymer.In a preferred embodiment of the invention, acrylic polymers is produced, it can be third The single polymer of alkene or propylene and at least one other ethylenically unsaturated monomer (such as ethene or C4-C20 alpha-olefins, especially C4-C20 alpha-olefins) combination polymer.The example of preferable alpha-olefin include ethene, propylene, butene-1, amylene -1, Hexene -1, heptene -1, octene-1, nonylene-1, decylene-1, dodecylene -1,4- methylpentenes -1,3- methylpentenes -1,3,5, 5- trimethylhexenes -1 and 5- ethyl nonylene-1s.

In a preferred embodiment of the invention, the polymer produced herein is the copolymerization of the homopolymer or ethene of ethene Thing, it preferably has 0-25mol%'s (alternatively 0.5-20mol%, alternatively 1-15mol%, preferably 3-10mol%) One or more C3-C20 olefin comonomers (preferably C3-C12 alpha-olefins, preferably propylene, butylene, hexene, octene, decene, ten Two carbenes, preferably propylene, butylene, hexene, octene).

In a preferred embodiment of the invention, the polymer produced herein is the copolymerization of the homopolymer or propylene of propylene Thing, it preferably has 0-25mol%'s (alternatively 0.5-20mol%, alternatively 1-15mol%, preferably 3-10mol%) One or more C2 or C4-C20 olefin comonomers (optimal ethylene or C4-C12 alpha-olefins, it is optimal ethylene, butylene, hexene, pungent Alkene, decene, dodecylene, optimal ethylene, butylene, hexene, octene).In a preferred embodiment of the invention, monomer is second Alkene, and comonomer is hexene, preferably 0.5-15mol% hexenes, alternatively 1-10mol%.

In some embodiments, polymer (such as ethylene copolymer or propylene copolymer) can also include and be based on monomer The at most 10 weight % of mixture, such as 0.00001-1.0 weight %, such as 0.002-0.5 weight %, such as 0.003-0.2 One or more diene of weight %.The non-limiting examples of useful diene include cyclopentadiene, norbornadiene, two rings penta Diene, 5- ethylidene -2- norbornene, 5- vinyl -2- norbornene, 1,4- hexadienes, 1,5- hexadienes, 1,5- heptan two Alkene, 1,6- heptadiene, 6- methyl isophthalic acids, 6- heptadiene, 1,7- octadienes, 7- methyl isophthalic acids, 7- octadienes, 1,9- decadinene, 1 and 9- Methyl isophthalic acid, 9- decadinene.

Final use

Using product made of the polymer produced herein can include for example moulding article (such as container and bottle, such as Household receptacle, industrial chemistry container, personal nursing bottle, containers for medical use, fuel tank and storage utensil, toy, sheet material, pipeline, Pipe), film, adhesive-bonded fabric etc..It should be appreciated that what list of application above was merely exemplary, it is not intended to restricted 's.

In a further embodiment, the present invention relates to：

1. (it is optionally used for alkene to gather by the pyridinylamino transition metal complex that formula (I), (II) or (III) represents Close)：

Wherein：

M is the race of the 3rd, 4 or 5 metal；

R¹Alkyl and polar group selected from alkyl, substitution；

Each R²And R³Independently selected from hydrogen, halogen, alkyl, the alkyl and polar group substituted, and R²And R³It can connect Conjunction forms ring；

Each R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³And R¹⁴Independently selected from hydrogen, halogen, alkyl, the hydrocarbon substituted Base and polar group, and any adjacent R group can engage formation can be with substituted or unsubstituted carbocyclic ring or miscellaneous The ring of ring；

R³And R⁴It can engage to form ring (preferably, engagement R³R⁴Group is-CH₂CH₂- five-membered ring, or engagement R¹⁰R¹¹Group is-CH₂CH₂CH₂- hexatomic ring)；

X and L groups can be engaged covalently；

N is 1,2 or 3；

Y is 0,1 or 2；

Wherein n+y is not more than 4.

2. the complex compound of paragraph 1, wherein M are Ti, Zr or Hf.

3. the complex compound of paragraph 1 or 2, wherein R²It is hydrogen, alkyl, aryl or halogen；And R³It is hydrogen, alkyl, aryl or halogen Element.

4. the complex compound of paragraph 1,2 or 3, wherein R¹It is described selected from the phenyl substituted by 0,1,2,3,4 or 5 substituent Substituent is selected from F, Cl, Br, I, CF₃、NO₂, alkoxy, dialkyl amido, alkyl and substituted alkyl, it is with 1-10 carbon Atom.

5. the complex compound of either segment in paragraph 1-4, wherein each L is independently selected from ether, thioether, amine, nitrile, imines, pyridine And phosphine.

6. the complex compound of either segment in paragraph 1-5, wherein each X is independently selected from halogen, alkyl, aryl, alkoxy, ammonia Base, hydride ion, phenoxy group, hydroxyl, alkyl azochlorosulfonate, carboxylate radical, silicyl, pi-allyl, alkenyl and alkynyl.

7. the complex compound of paragraph 1, wherein, R¹It is 2- aminomethyl phenyls, 2- isopropyl phenyls, 2- ethylphenyls, 2,6- diformazans Base phenyl,One kind or more in base, 2,6- diethyl phenyls, 2,6- diisopropyl phenyls and 2,4,6- triisopropyl phenyl Kind.

8. the complex compound of paragraph 1, wherein M are Zr or Hf, R²And R³All it is hydrogen, and J is the aromatic carbon containing 6-14 carbon Ring.

9. the complex compound of paragraph 1, wherein, M is group-4 metal, R²For hydrogen, R³And R⁴Engagement forms 5 yuan of rings, wherein R³R⁴It is single Member is-CH₂CH₂-。

10. the complex compound of paragraph 1, wherein, M is group-4 metal, R²For hydrogen, R³And R⁴Engagement forms 6 yuan of rings, wherein R³R⁴ Unit is-CH₂CH₂CH₂-。

11. include the catalyst system of the transition metal complex of either segment in activator and paragraph 1-10.

12. the catalyst system of paragraph 11, wherein the activator includes non-coordinating anion and/or aikyiaiurnirsoxan beta.

13. the catalyst system of paragraph 11 or 12, wherein the catalyst system is load.

14. the catalyst system of paragraph 11,12 or 13, wherein the complex compound is represented by formula (A) or (B)：

15. the system of either segment in paragraph 11-14, wherein the transition metal complex is load.

16. preparing the polymerization of polyolefin, it includes making one or more olefinic monomers and either segment in paragraph 11-15 Catalyst system contact and obtain olefin polymer.

17. the method for paragraph 16, wherein the monomer includes ethene and/or propylene.

18. the complex compound being expressed from the next：

Wherein：

M is the race of the 3rd, 4 or 5 metal；Q is-(TT)-or-(TTT)-, wherein each T be the substituted or unsubstituted 14th, 15 or 16 race's elements so that it forms 5- or 6- circle heterocycles together with "-C-N=C- " fragment；R¹Alkyl selected from alkyl, substitution And polar group；Each R²And R³Independently selected from hydrogen, halogen, alkyl, the alkyl and polar group substituted, and R²And R³Can Ring is formed with engagement；Each R⁴、R⁵、R⁶And R⁷Independently selected from hydrogen, halogen, alkyl, the alkyl and polar group substituted, and Any adjacent R group can engage the ring to form the carbocyclic ring that can be substituted or unsubstituted or heterocycle；R³And R⁴Shape can be engaged Cyclization, or R¹⁰And R¹¹It can engage to form ring；HJ is the noncoordinating aromatic group containing 4-40 carbon atom, it can go Protonation is coordinated to the group of metal center to be formed by carbanion donor；

Each X is anion leaving group, and wherein X group can be identical or different, and any two X group can connect Connect to form dianion leaving group；Each L is neutral Lewis base, and any two L groups can engage to form bidentate Lewis base；X and L groups can be engaged covalently；N is 1,2 or 3；Y is 0,1 or 2；Wherein n+y is not more than 4.

Experiment

Using the solution by dissolving about 10mg (about 0.2M) sample preparation in C6D6, obtained in 400MHz¹H NMR light Modal data.Given chemical shift (δ) is relative to the remaining protium in the deuterated solvent at 7.15ppm.

Embodiment

The instantiation of the ligand prepared is as follows：

The instantiation of the pre-catalyst complex compound prepared is as follows：

Described below for the synthetic route for preparing complex compound B.Replaced in a similar way using the bromo- 6- naphthlypyridines of 2- The bromo- 6- phenylpyridines of 2- have synthesized complex compound A.

The synthesis of the bromo- 6- phenylpyridines of 2-.By butyl lithium (50mL, 118mmol), hexane (100mL) and dimethylamino Ethanol (5.91mL, 59.0mmol) merges, and is cooled to -10 DEG C, be added dropwise in 5 minutes 2- phenylpyridines (7.63g, 49.2mmol) with the orange solution of formation clarification.1 it is small when after, solution has been deepened as reddish orange.Then the solution is cooled down To -40 DEG C, and addition has cooled to -35 DEG C of THF (500mL).Once add immediately 1,2- Bromofumes (25.4mL, 295mmol), and by mixture it is warmed to environment temperature.Volatile matter is removed by evaporating, and yellow oily paste is dissolved in Et₂O In (125mL) and water (100mL).With brine and then with sodium sulphate, water layer is removed, organic matter is dried.Ether is evaporated, is obtained Crude product, it is crystallized from hexane, is yellow crystals (8.0g, 69%).

The synthesis of 2,6- diisopropyls-N- ((1- (6- phenylpyridine -2- bases) naphthalene -2- bases) methyl) aniline (1).By carbonic acid Sodium (0.567g, 5.35mmol) is dissolved in MeOH (20ml) and water (80ml), uses N₂Bubbling 30 minutes.By resulting solution in N₂Gas The bromo- 6- phenylpyridines (0.476g, 2.03mmol) of 2- for being dissolved in toluene (75ml), 2,6- diisopropyls-N- are added under atmosphere ((1- (4,4,5,5- tetramethyls -1,3,2- dioxaborolanes -2- bases) naphthalene -2- bases) methyl) aniline (0.904g, 2.04mmol) and Pd (PPh₃)₄In the mixture of (0.124g, 0.107mmol).By mixture be heated to reflux 12 it is small when, and then It is cooled to room temperature.With brine and then with sodium sulphate, organic layer is separated, it is dry, and remove solvent.Use hexane-EtOAc (20:1, v/v) eluent is used as, passes through silica gel column chromatography separation product.Obtain white solid product (0.630mg, 66%).

2,6- diisopropyls-N- (the synthesis of (2- (6- phenylpyridine -2- bases) benzyl) aniline (2).By sodium carbonate (0.445g, 4.20mmol) is dissolved in MeOH (25ml) and water (75ml), and uses N₂Bubbling 30 minutes.By resulting solution in nitrogen The bromo- 6- phenylpyridines (0.392g, 1.67mmol) of 2- for being dissolved in toluene (60ml), 2,6- diisopropyls-N- are added under atmosphere ((2- (4,4,5,5- tetramethyls -1,3,2- dioxaborolanes -2- bases) benzyl) aniline (0.660g, 1.67mmol) and Pd (PPh₃)₄In the mixture of (0.115g, 0.099mmol).By mixture be heated to reflux 12 it is small when, be subsequently cooled to room temperature.Use salt Water and then with magnesium sulfate, organic layer is separated, dry, and removes solvent.Use hexane-EtOAc (50:1, v/v) as elution Liquid, by silica gel column chromatography separation product, obtains product (0.619mg, 88%).

The synthesis of complex compound A.Toluene (10mL) is added to ligand 1 (0.207g, 0.440mmol) and tetrabenzyl hafnium In (0.263g, 0.484mmol).Heat the mixture to 100 DEG C, while shading.15 it is small when after, evaporating volatile substances, to obtain Residue, it is fully washed with pentane, to obtain the yellow-orange solid of complex compound A (0.30g, 81%).

The synthesis of complex compound B.By the mixture of dodecane (5mL) and toluene (1mL) be added to ligand 2 (0.228g, 0.542mmol) and in four (dimethylamino) hafniums (0.192g, 0.542mmol).The mixture is heated to 150 DEG C.16 it is small when Afterwards, evaporating volatile substances, to obtain double (amino) complex compound [(ligand (2)) Hf (NMe₂)₂], be yellow-orange solid (0.355g, 95.6%).The part (0.274g, 0.400mmol) of double (amino) complex compounds is merged with toluene (8mL) and is hanged with forming yellow Supernatant liquid.Then trimethyl aluminium (0.288g, 4.00mmol) was added dropwise in one minute.Heat the mixture to 50 DEG C 30 minutes, and Then evaporating volatile substances under nitrogen flowing.Product is washed with pentane and is dried under reduced pressure (0.14g, 56%).

Polymerization Example.

Olefinic polymerization carries out in high-throughput (throughput) pressure reactor in parallel, such as in US 6,306,658； US 6,455,316；US 6,489,168；WO 00/09255；With Murphy et al., J.Am.Chem.Soc., the 2003, the 125th Roll up, general description, therein to be each fully incorporated herein by quoting in the 4306-4317 pages, as long as and this specification Not contradiction.General procedure for screening catalyst is described below.Chemicals used (such as it is pre-catalyst, activator, clear Except agent, chain-transferring agent etc.) required temperature, pressure, amount will change with experiment, and concrete numerical value is given in the table below, its In provide data.

The vial plug-in unit weighed in advance and disposable agitating paddle are installed to each reaction vessel of reactor, it is wrapped Containing 48 single reaction vessels.Reactor is then shut off, each container is separately heated to required temperature and is forced into predetermined Pressure (being usually 75psi=0.517MPa).If desired, 1- octenes are then injected into by each reaction vessel by valve In, enough solvents (being typically isohexane or toluene) are then added, so that total reaction volume (including subsequent charging) reaches Required volume (being usually 5mL).Then the content of container is stirred at 800 rpm.Then by the solution of scavenger (usually It is organoaluminum reagents in isohexane or toluene) added together with solvent tracer (chaser) (usual 500 microlitres).If need Will, then the solution of other scavenger or chain-transferring agent is added together with solvent tracer (usual 500 microlitres).Then will (usual 500 is micro- with solvent tracer for activator solution (being commonly angled relative to 1 molar equivalent of pre-catalyst complex compound) in toluene Rise) it is injected into together in reaction vessel.Then by the toluene solution of the pre-catalyst complex compound of dissolving and solvent tracer (usually 500 microlitres) add together.

Then carry out reaction, until polymerisation has consumed the ethylene pressure of set amount (for being carried out under 75psi Reaction be usually 12psi=0.137MPa) or had been subjected to specific time quantum (be usually 10-20 minutes).At this time, pass through Reaction is quenched container pressurization with compressed air.After polymerization, it is the glass containing polymer product and solvent is small Bottle plug-in unit takes out from balancing gate pit and inert-atmosphere glove box, and uses Genevac HT-12 centrifuges and Genevac VC3000D cold boilers (operating at elevated temperature and reduced pressure) remove volatile component.Then bottle is weighed to determine polymer The yield of product.Resulting polymers are analyzed by quick GPC (seeing below) to determine molecular weight.

In order to determine various molecular weight correlation values by GPC, " quick GPC " the systems progress high-temperature body of automation is used Product exclusion chromatography.The instrument has the linear columns of three 30cm × 7.5mm a series of, and each column contains 10 μm of PLgel, mixes Close B.Polystyrene standards of the use scope in 580g/mol-3,390,000g/mol correct GPC system.The system exists Run under the eluent flow rate of 2.0mL/min and 165 DEG C of oven temperature.Eluent is used as using 1,2,4- trichloro-benzenes.Will be poly- Compound sample is dissolved in 1,2,4- trichloro-benzenes with the concentration of 0.1-0.9mg/mL.250 μ L polymer solutions are injected into system In.The concentration of polymer in eluent is monitored using evaporative light scattering detector.The molecular weight provided in embodiment is opposite In linear polystyrene reference material.

Differential scanning calorimetry (DSC) measurement is carried out on TA-Q100 instruments to determine the fusing point of polymer.Sample is existed 220 DEG C of preannealings 15 minutes, and it is subsequently cooled to ambient temperature overnight.Then sample is heated to 220 with 100 DEG C/min of speed DEG C, and then cooled down with 50 DEG C/min of speed.Fusing point is collected during heating.

As shown by data shown in table 1, the activated complex of heretofore described general type being capable of olefin polymerization.Table 1 shows the polymerization result and polymer characterization data with activated complex A and B the ethylene-octene copolymerization carried out.Run 1-6 Condition it is as follows：80 DEG C of polymerization temperature, isohexane solvent, cumulative volume=5mL, 75psi ethene, the amount of complex compound A or B are 20nmol, activator are n,N-DimethylanilineFour (pentafluorophenyl group) borates, and activator/complex compound ratio are 1:1.

Table 1

All Files described herein is incorporated herein by reference, including any priority document and/or test journey Sequence, as long as them and not contradiction herein.Although it is apparent that having been described above from foregoing general description and specific embodiment With the form that the invention has been described, but various modifications can be carried out without departing from the spirit and scope of the present invention. Therefore, it is not intended to thus limit the present invention.Equally, term "comprising" is considered synonymous with term " comprising ".Similarly, no matter what When composition, key element or key element group before carry conjunction "comprising", it is thus understood that we have also contemplated that it is described form, one Kind or the record of a variety of key elements before with conjunction " substantially by ... form ", " by ... form ", " be selected from By ... the group formed " or the identical of "Yes" form and the group of key element, vice versa.

Claims

1. the transition metal complex represented by formula (I)：

Wherein：

M is the race of the 3rd, 4 or 5 metal；

Q is-(TT)-or-(TTT)-, wherein each T is the race's element of the substituted or unsubstituted 14th, 15 or 16 so that it with "-C-N=C- " fragment forms 5- or 6- circle heterocycles together；

R¹Alkyl and polar group selected from alkyl, substitution；

Each R²And R³Independently selected from hydrogen, halogen, alkyl, the alkyl and polar group substituted, and R²And R³Shape can be engaged Cyclization；

Each R⁴、R⁵、R⁶And R⁷Independently selected from hydrogen, halogen, alkyl, substitution alkyl and polar group, it is and any adjacent R group can engage that to be formed can be with substituted or unsubstituted carbocyclic ring or the ring of heterocycle；

R³And R⁴It can engage to form ring；

Each X is anion leaving group, and wherein X group can be identical or different, and any two X group can connect shape Into dianion leaving group；

X and L groups can be engaged covalently；

N is 1,2 or 3；

Y is 0,1 or 2；

Wherein n+y is not more than 4.

2. complex compound according to claim 1, wherein the complex compound is represented by Formula II：

Wherein：

M is the race of the 3rd, 4 or 5 metal；

R¹Alkyl and polar group selected from alkyl, substitution；

Each R⁴、R⁵、R⁶、R⁷、R⁸、R⁹And R¹⁰Independently selected from hydrogen, halogen, alkyl, the alkyl and polar group substituted, and Any adjacent R group can engage that to be formed can be with substituted or unsubstituted carbocyclic ring or the ring of heterocycle；

R³And R⁴It can engage to form ring；

X and L groups can be engaged covalently；

N is 1,2 or 3；

Y is 0,1 or 2；

Wherein n+y is not more than 4.

3. complex compound according to claim 1, wherein the complex compound is represented by formula III：

Wherein：

M is the race of the 3rd, 4 or 5 metal；

R¹Alkyl and polar group selected from alkyl, substitution；

Each R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³And R¹⁴Independently selected from hydrogen, halogen, alkyl, the alkyl of substitution and pole Property group, and any adjacent R group can engage that to be formed can be with substituted or unsubstituted carbocyclic ring or the ring of heterocycle；

R³And R⁴It can engage to form ring, and R¹⁰And R¹¹It can engage to form ring；

X and L groups can be engaged covalently；

N is 1,2 or 3；

Y is 0,1 or 2；

Wherein n+y is not more than 4.

4. according to the complex compound described in claim 1,2 or 3, wherein M is Ti, Zr or Hf.

5. according to the complex compound described in claim 1,2 or 3, wherein R²It is hydrogen, alkyl, aryl or halogen；And R³It is hydrogen, alkane Base, aryl or halogen.

6. complex compound according to claim 3, wherein R¹Contain 1-30 carbon atom.

7. according to the complex compound described in claim 1,2 or 3, wherein R¹Selected from the benzene substituted by 0,1,2,3,4 or 5 substituent Base, the substituent are selected from F, Cl, Br, I, CF₃、NO₂, alkoxy, dialkyl amido, alkyl and substituted alkyl, it is with 1- 10 carbon atoms.

8. according to the complex compound described in claim 1,2 or 3, wherein each L is independently selected from ether, thioether, amine, nitrile, imines, pyrrole Pyridine and phosphine.

9. according to the complex compound described in claim 1,2 or 3, wherein each X is independently selected from halogen, alkyl, aryl, alcoxyl Base, amino, hydride ion, phenoxy group, hydroxyl, alkyl azochlorosulfonate, carboxylate radical, silicyl, pi-allyl, alkenyl and alkynyl.

10. according to the complex compound described in claim 1,2 or 3, wherein R¹It is 2- aminomethyl phenyls, 2- isopropyl phenyls, 2- ethylo benzenes Base, 2,6- 3,5-dimethylphenyls,In base, 2,6- diethyl phenyls, 2,6- diisopropyl phenyls and 2,4,6- triisopropyl phenyl One or more.

11. according to the complex compound described in claim 1,2 or 3, wherein M is Sc, Y, Ti, Zr, Hf, V, Nb or Ta.

12. complex compound according to claim 1 or 2, wherein M are Zr or Hf, R²And R³All it is hydrogen, and J is containing 6-14 The aromatic carbocyclic of a carbon.

13. according to the complex compound described in claim 1,2 or 3, wherein, M is group-4 metal, R²For hydrogen, R³And R⁴Engagement forms 5 Yuan of rings, wherein R³R⁴Unit is-CH₂CH₂-。

14. according to the complex compound described in claim 1,2 or 3, wherein, M is group-4 metal, R²For hydrogen, R³And R⁴Engagement forms 6 Yuan of rings, wherein R³R⁴Unit is-CH₂CH₂CH₂-。

15. the catalyst system comprising activator and the transition metal complex according to any one of claim 1-14.

16. catalyst system according to claim 15, wherein the activator includes non-coordinating anion.

17. catalyst system according to claim 15, wherein the activator includes aikyiaiurnirsoxan beta.

18. catalyst system according to claim 15, wherein the catalyst system is load.

19. catalyst system according to claim 15, wherein the complex compound is represented by formula (A) or (B)：

20. preparing the polymerization of polyolefin, it includes making one or more olefinic monomers with appointing according in claim 15-19 Catalyst system contact and acquisition olefin polymer described in one.

21. according to the method for claim 20, wherein the activator includes aikyiaiurnirsoxan beta.

22. according to the method for claim 20, wherein the activator includes non-coordinating anion.

23. according to the method for claim 20, wherein the monomer includes ethene and/or propylene.

24. according to the method for claim 20, wherein the transition metal complex is load.

25. the complex compound being expressed from the next：

Wherein：

M is the race of the 3rd, 4 or 5 metal；

R¹Alkyl and polar group selected from alkyl, substitution；

R³And R⁴It can engage to form ring or R¹⁰And R¹¹It can engage to form ring；

HJ is the noncoordinating aromatic group containing 4-40 carbon atom, it can be with deprotonation to be formed by carbanion donor It is coordinated to the group of metal center；

X and L groups can be engaged covalently；

N is 1,2 or 3；

Y is 0,1 or 2；

Wherein n+y is not more than 4.