CN106029675A - Pyridyldiamido transition metal complexes, production and use thereof - Google Patents

Abstract

Pyridyldiamido transition metal complexes are disclosed for use in alkene polymerization to produce high melting point polyolefins.

Description

Pyridine radicals diaminourea transition metal complex, its preparation and purposes

Inventor: John R.Hagadorn and Patrick J.Palafox

Priority

USSN 61/947,052 that application claims was submitted on March 3rd, 2014 and in 2014 The priority of the EP application 14168393.8 that on May 15, in submits to and rights and interests.

Technical field

The present invention relates to pyridine radicals diaminourea (pyridyldiamido) transition metal complex and manufacture The intermediate of this kind of pyridine radicals diaminourea complex and method.Described transition metal complex can be used Make the catalyst of olefine polymerizing process.

Background technology

Pyridine radicals amine has been used for preparing the 4th group complex, and described complex is for olefinic polymerization Useful transition metal component, see for example US 2002/0142912, US 6,900,321 He US 6,103,657, wherein said part has been used to wherein said part by bidentate mode and transition The complex of metallic atom coordination.

WO 2005/095469 shows catalyst compounds, and described compound is via two nitrogen-atoms (amino and a pyridine radicals) and an oxygen atom use tridentate ligand.

US 2004/0220050A1 and WO 2007/067965 disclose wherein part by three tooth modes Via two nitrogen (amino and a pyridine radicals) and carbon (aryl anion) donative ligand Complex.

Committed step in the activation of these complex be alkene be inserted into the metal of catalyst precarsor- In aryl key (Froese, R.D.J. et al., J.Am.Chem.Soc.2007,129,7831-7840) To form the active catalyst with 5 yuan and 7 yuan two kinds of chelate rings.

WO 2010/037059 discloses the amine containing pyridine for medicinal application.

US 2012/0071616 A1 discloses the pyridine radicals diamine catalyst complexation comprising NNN part Thing, this NNN part has neutral pyridine donor and two anionic amino donors, this anion ammonia Base donor replaces phenyl and 2,6-diisopropyl phenyl, but does not contain 1-20 carbon atom and have There is the hydrocarbon of 1.66 or higher H/C ratios (wherein the carbon atom with nitrogen keyed jointing is not tertiary carbon atom) Base.

Other list of references of interest includes: Vaughan, A；Davis,D.S.； Hagadorn,J.R.in Comprehensive Polymer Science,Vol.3,Chapter 20, “Industrial catalysts for alkene polymerization；”Gibson,V.C.； Spitzmesser,S.K.Chem.Rev.2003,103,283；Britovsek,G.J.P.； Gibson,V.C.；Wass,D.F.Angew.Chem.Int.Ed.1999,38,428；US 7,973,116；US 7,446,216；US 7,812,104；US 7,276,567；US 7,667,064；US 7,868,197；US 7,557,171；US 7,538,168；US 2011/0224391；US 2011/0301310；In the USSN that on April 23rd, 2013 submits to 61/815065；US 2010/0227990 (it is noted that catalyst structure with there is NNC donor group Metal center keyed jointing)；WO/0238628 A2 (it is noted that part with there is NNC donor group Metal center keyed jointing)；And Guerin, F.；McConville,D.H.；Vittal, J.J.Organometallics 1996,15,5586 is not (it is noted that NNN-donor group contains 7 yuan Chelate ring or dihydro indenyl and/or tetralyl).

Remain a need for increasing synthetic route to widen scope and the increasing of the catalyst complex that can prepare They performances in olefin polymerization wide.Described performance can change in the following areas: prevailing The amount (normally referred to as " active ") of polymer prepared by the catalyst of unit quantity under polymerizing condition；? The molecular weight and molecualr weight distribution reached at given temperature；With in terms of the degree that stereoregular configures The configuration of high alpha-olefin.

It addition, what the catalyst productivity improved was desirable to, because it reduces the one-tenth using catalyst This.Additionally, preparation high molecular, the single-site catalysts of high crystalline polypropylene are precious, Remain on the polypropylene wishing preparation containing high stiffness product.

This demand is solved by new pyridine base diamidogen (PDA) catalyst disclosed herein.? In propylene polymerization research, find that these catalyst not only have the activity of improvement but also prepare higher melt Polymer.

Summary of the invention

Brief summary of the invention

The present invention relates to the novel transition metal complex with three tooth NNN or PNN part.This The bright pyridine radicals diaminourea further relating to be represented by formula (A), (B), (I) or (II) and corresponding transition gold Genus complex:

Wherein:

M is the 3rd, 4,5,6,7,8,9,10,11 or 12 race's metals；

Q1 is by preferably by formula-G¹-G²-G³Three atomic bridges of-expression are by R²The group connected with Z, The center of wherein said three atoms is preferably to form the 15th or 16 race's elements of coordinate bond with M, Wherein G²It is the atom of the 15th or 16 races, G¹And G³It is respectively the atom of the 14th, 15 or 16 races, Wherein G¹、G²And G³, or G¹And G², or G¹And G³, or G²And G³Monocycle or multi-ring can be formed System, if G¹And/or G³In any one be the atom of the 14th race, then R³⁰And R³¹Bonding On this kind of one or more G atoms, if G¹、G², and/or G³In any one be The atom of 15 races, then R³⁰It is bonded on this kind of one or more G atoms, the most each R³⁰And R³¹ Independently be hydrogen or C₁-C₁₀₀Alkyl；

Q2 is NR¹⁷Or PR¹⁷, wherein R¹⁷Selected from having 1.66 or bigger containing 1-20 carbon atom The alkyl of H/C ratio, wherein the carbon atom with N or P keyed jointing is not tertiary carbon atom, and wherein R¹⁷ Can be unsubstituted or substituted；

Q3 is-(TT)-or-(TTT)-, the most each T is carbon or hetero atom (preferably C, O, S Or N, described carbon or hetero atom can be unsubstituted (such as, hydrogen with carbon or hetero atom keyed jointing) or Replace and have one or more R³⁰Group), these one or more R³⁰Group and "-C-Q³=C-" fragment Form 5-or 6-cyclic group together or include the polycyclic moiety of described 5 or 6 cyclic group；

R1 is selected from alkyl and substituted alkyl or silicyl；

R²And R¹⁰It is-E (R independently of one another¹²)(R¹³)-, wherein E is carbon, silicon or germanium, each R¹² And R¹³Independently selected from hydrogen, alkyl and substituted alkyl, alkoxyl, silicyl, amino, Aryloxy group, halogen and phosphino-(phosphino), R¹²And R¹³Can engage to form saturated, replacement Or unsubstituted alkyl ring, wherein this ring has 4,5,6 or 7 ring carbon atoms and wherein this ring On substituent group can engage to form additional ring, or R¹²And R¹³Can engage to be formed saturated Heterocycle or saturated substituted heterocycle, wherein the substituent group on this ring can engage to be formed additional Ring；

Z is-(R₁₄)pC-C(R₁₅) q-and R₁₄And R₁₅Independently selected from hydrogen, alkyl and substituted hydrocarbon Base, and the most adjacent R₁₄And R₁₄Base can engage form aromatics or saturated, replacement or do not take The alkyl ring in generation, wherein this ring has 5,6,7 or 8 ring carbon atoms and wherein taking on this ring Can engage to form additional ring for base, p is 1 or 2, and q is 1 or 2；

L is anion leaving group, and wherein this L group can be identical or different and any two L group can connect to form dianion leaving group；

N is 0,1,2,3 or 4；

L' is neutral Lewis base；With

W is 0,1,2,3 or 4；

Wherein n+w is at most 4；

R³、R⁴And R⁵Independently selected from hydrogen, alkyl, substituted alkyl, alkoxyl, aryloxy group, Halogen, amino and silicyl, and the most adjacent R group (R³&R⁴And/or R⁴&R⁵) can To engage to form substituted or unsubstituted alkyl or the ring of heterocycle, wherein this ring has 5,6,7 Or 8 annular atomses and wherein the substituent group on this ring can engage to form additional ring；With

R⁶、R⁷、R⁸、R⁹、R^15*And R^16*Independently selected from hydrogen, alkyl, substituted alkyl, alcoxyl Base, halogen, amino and silicyl, and the most adjacent R group (R⁶&R⁷, and/or R⁷& R^15*, and/or R^16*&R^15*, and/or R⁸&R⁹) can engage form saturated, replacement or do not take The alkyl in generation or the ring of heterocycle, wherein this ring has 5,6,7 or 8 ring carbon atoms and wherein should Substituent group on ring can engage to form additional ring.

The invention still further relates to use catalyst described herein to prepare polyolefin, the most polyacrylic side Method, wherein said catalyst has the activity of 200kg polymer/mmol catalyst/h or bigger.

The method that the invention still further relates to prepare above-mentioned complex, preparation is for the centre of above-mentioned complex The method that the method for body and the above-mentioned complex of use make olefinic polymerization, wherein said complex has The activity of 200kg polymer/mmol catalyst/h or bigger.

Accompanying drawing is sketched

Fig. 1 is the catalyst of the catalyst showing the activation formation by complex A, B, C and D The drawing of activity (with kg polymer/mmol catalyst/h as unit).

Detailed Description Of The Invention

Present specification describes transition metal complex.Term " complex " is used for describing wherein assisting The molecule that part is coordinated with central transition metal atom.Part be huge (bulky) and and transition Stabilized metal ground keyed jointing is so that maintaining its impact during catalyst application (such as polymerization).Part Can be by covalent bond and/or give electron coordinate or intermediate bond (intermediate bond) and transition Metal-complexing.Generally using activator makes transition metal complex experience activation play the poly-of them Close or oligomeric function, it is believed that described transition metal complex due to anionic group (commonly referred to " from Group ") is gone to produce cation from removing of transition metal.

Except as otherwise noted, room temperature is 23 DEG C.

The new numbering plan of each race of the periodic table of elements used herein is Chemical and Engineering News, 63 (5), the new annotation be given in 27 (1985).

Me used herein is methyl, and Et is ethyl, and Bu is butyl, t-Bu and^tBu is uncle Butyl, Pr is propyl group, iPr andⁱPr is isopropyl, and Cy is cyclohexyl, THF (also referred to as thf) Being oxolane, Bn is benzyl, and OAc is acetas (salt) and Ph is phenyl.

Term " replaces " and generally refers to be replaced the hydrogen of material with different atoms or atomic group Replace.Such as, methyl-cyclopentadiene is the cyclopentadiene replacing and having methyl.Similarly, picric acid Can be described as replacing the phenol having three nitros, maybe can also be described as replacement have a hydroxyl and The benzene of three nitros.

Term " alkyl (hydrocarbyl radical) ", " alkyl (hydrocarbyl) " and " alkyl (hydrocarbyl group) " is interchangeably used in whole file.Similarly, art Language " group ", " base " and " substituent group " is the most also interchangeably used.To these public affairs For opening content, " hydrocarbyl group " is defined as C₁-C₁₀₀Group, its can be linear, branched or Ring-type, and when being ring-type, be aromatics or non-aromatic.

Substituted alkyl is that at least one hydrogen atom of wherein alkyl has been substituted at least one official Such as NR can be rolled into a ball^* ₂、OR^*、SeR^*、TeR^*、PR^* ₂、AsR^* ₂、SbR^* ₂、SR^*、BR^* ₂、SiR^* ₃、 GeR^* ₃、SnR^* ₃、PbR^* ₃Deng or at least one of which hetero atom have been inserted in alkyl ring.

Term " catalyst system " is defined as referring to complex/activator pair.When " catalyst system " When being used for this kind of pairing described before activation, it refers to that non-activated catalyst complex (is urged in advance Agent) together with activator and, optionally, conactivator.When it is used for describing after the activation During this kind of pairing, it refers to complex and activator or other charge balance structure part of activation. Transistion metal compound can be neutral, as in pre-catalyst, or has counter ion counterionsl gegenions Charged class material, as in activated catalyst systems.

" complex " used herein be also commonly referred to as catalyst precarsor, pre-catalyst, catalyst, Catalyst compounds, transistion metal compound or transition metal complex.These words are interchangeably Use.Activator and promoter are also interchangeably used.

Scavenger is generally to be added the compound for being promoted polymerization by removal of contamination.Some are clear Except agent can also serve as activator and is properly termed as conactivator.It it not the conactivator of scavenger Can also be used in combination to form active catalyst with activator.In some embodiments, permissible By conactivator with transistion metal compound premixing to form alkylating transistion metal compound.

Non-coordinating anion (NCA) is defined to refer to be unworthy of being positioned at catalyst metals cation or coordination But the anion in the most weak coordination of described metal cation.Term NCA is further defined as including The multicomponent containing acid cation group and the non-coordinating anion activator containing NCA, such as four (five Fluorophenyl) boric acid N, N-dimethyl puratized agricultural spray.Term NCA is further defined as including passing through anion The extraction of group forms the neutral lewis acid of activating substance, such as three (phenyl-pentafluorides with catalyst reaction Base) boron.NCA is coordinated the most weakly so that neutral Lewis base, such as olefinic or acetylene series unsaturation list Body can replace it from catalyst center.Any gold of the complex of coordination compatible, weak can be formed Belong to or metalloid can use or be included in non-coordinating anion.Suitable metal includes, but does not limits In aluminum, gold and platinum.The metalloid being suitable for includes, but not limited to boron, aluminum, phosphorus and silicon.Chemistry Metering activator can be neutral or ion-type.Term ionic activator and stoichiometric from Subtype activator can be interchangeably used.Similarly, term neutral stoichiometric activator and road Lewis acid activator can be interchangeably used.Term non-coordinating anion includes neutral stoichiometric Activator, ionic stoichiometric activator, ionic activator and Lewis acid activation agent.

" alkene ", or be referred to as " olefin(e) " be carbon and hydrogen have at least one double bond linear, Branched or cyclic compound.For this specification and claims thereof, when polymer or common Polymers is referred to as olefin-containing, and the alkene being present in this base polymer or copolymer is the poly-of described alkene Conjunction form.Such as, when copolymer is said to be " ethylene " content with 35wt%-55wt%, It should be understood that monomeric unit in described copolymer derived from the ethylene in polyreaction and Described derivative unit is pressed 35wt%-55wt% and is existed, weight based on described copolymer." poly- Compound " there is two or more identical or different monomeric units." homopolymer " is containing identical The polymer of monomeric unit." copolymer " is to have two or more monomer lists different from each other The polymer of unit." terpolymer " is the polymer with three kinds of monomeric units different from each other. Indicate described monomeric unit to differ each other to be at least for relating to the term " different " of monomeric unit One atom or isomery are different.Therefore, the definition of copolymer used herein includes ternary Copolymer and analog.Oligomer is typically have low-molecular-weight, and (such as Mn is less than 25,000 G/mol, preferably smaller than 2,500g/mol) or low monomeric unit number (such as 75 monomeric units or Polymer less)." ethene polymers " or " ethylene copolymer " is to comprise at least 50mol% The polymer of the unit of ethylene derivative or copolymer, " acrylic polymers " or " propylene copolymer " It is polymer or the copolymer of the unit comprising at least 50mol% propylene derived, like this.

For the present invention, ethylene is considered as alpha-olefin.

High alpha-olefin or senior alkyl are defined as containing 4 or the alpha-olefin of more carbon atom.

Unless otherwise mentioned, all molecular weight units (such as, Mw, Mn, Mz) are g/mol.

Unless otherwise mentioned, all fusing points (Tm) are DSC second melting fusing points.

" ring carbon atom " is belonging to the carbon atom of a part for cyclic rings structure.According to this definition, Benzyl has six ring carbon atoms, and p-methylstyrene also has six ring carbon atoms.

Term " aryl " refers to six carbon aromatic rings and its substituted variant, includes but not limited to, phenyl, The bromo-xylyl of 2-methylphenyl, xylyl, 4-.Similarly, heteroaryl refers to its medium ring Hetero atom used by carbon atom (or two or three ring carbon atoms), the virtue that preferably N, O or S replace Base.

Term " annular atoms " refers to belong to the atom of a part for cyclic rings structure.Certain according to this Justice, benzyl has 6 annular atomses, and oxolane has 5 annular atomses.

Heterocycle is to have heteroatomic ring in ring structure, is replaced by hetero atom with the hydrogen on wherein annular atoms The substituted ring of hetero atom in generation is different.Such as, oxolane is heterocycle, 4-N, N-dimethylamino- Phenyl is the substituted ring of hetero atom.

Term " aromatics " refers to benzene and benzene derivate, and it is to have three rings replacing double bond In containing the cyclic hydrocarbon group of six carbon.Term as used herein " aromatics " goes back finger ring pentadiene or standard Aromatics (pseudoaromatic) heterocycle, they be have with aromatic heterocycle part similar performance and Structure (almost plane), but the heterocyclic substituent of aromatics it is not belonging to according to definition；Similarly, art Language aromatics also refers to substituted aromatic compounds.

Term " continuously " refers to the system of operation in the case of not having interrupting or stopping.Such as, system The continuation method of standby polymer will be that wherein reactant is introduced continuously into one or more reactor also And the method that polymer product is continuously withdrawn.

Polymerisation in solution refers to that wherein polymer is dissolved in liquid polymerizaton medium, such as atent solvent or monomer (one or more) or the polymerization of their blend.Polymerisation in solution is typically homogeneous.All Phase-polymerization is the polymerization during wherein polymer product is dissolved in polymerisation medium.Such system is the most not It is muddy, such as J.Vladimir Oliveira, C.Dariva and J.C.Pinto, Ind. Eng, Chem.Res.29,2000, p.4627 described in.

Polymerisation in bulk refers to that the monomer being the most just polymerized and/or comonomer are used as solvent or dilution Agent and use with little or no use atent solvent as solvent or the polymerization of diluent.Small part Atent solvent possibly serves for the carrier of catalyst and scavenger.Bulk polymerization system typically contains little In atent solvent or the diluent of 25wt%, preferably smaller than 10wt%, preferably smaller than 1wt%, excellent Select 0wt%.

When being used for describing polymer or polymer composition, term " many kurtosis " refers to that " many kurtosis divide Son amount distribution ", it is understood to refer to gel permeation chromatography (GPC) trace, is plotted as absorbance pair The curve of the time of staying (second), has more than one peak or flex point." flex point " is wherein curve The point (such as, from negative to positive, vice versa) that second dervative sign changes.Such as, including One low-molecular weight polymer component (such as there is the polymer of the Mw of 100,000g/mol) and second The polyolefin of high molecular weight polymer components (such as there is the polymer of the Mw of 300,000g/mol) Compositions is considered " bimodal " polyolefin composition.Preferably, polymer or polymer composition Mw differs at least 10% each other, preferably differs at least 20%, preferably at least 50%, preferably At least 100%, preferably at least 200%.Similarly, in a preferred embodiment, polymerization The Mw of thing or polymer composition differs 10%-10 each other, and 000%, preferably 20% -1000%, preferably 50%-500%, preferably at least 100%-400%, preferably 200%-300%.

Unless otherwise stated, " catalyst activity " is to use to comprise W mmol transition metal (M) Polymerization catalyst within the period of T hour, prepare measuring of how many kg of polymer (P)；And can With by with following formula: P/ (T × W) represents.

The pyridine radicals diamino represented by formula (A) or (B) is provided in the first aspect of the invention Base transition metal complex (is optionally used for olefinic polymerization):

Wherein:

M is the 3rd, 4,5,6,7,8,9,10,11 or 12 race's metals, the preferably the 4th race；

Q1 is by preferably by formula-G¹-G²-G³Three atomic bridges of-expression are by R²The group connected with Z, The center of wherein said three atoms is preferably to form the 15th or 16 race's elements of coordinate bond with M, Wherein G²It is the 15th or 16 race's atoms (preferably N, S, P or O, preferably N or P, preferably N), G¹And G³Being individually the 14th, 15 or 16 race's atoms, preferably C, Si, N, S, P or O are (preferably C), wherein G¹、G²And G³, or G¹And G², or G¹And G³, or G²And G³Can be formed monocycle or Polycyclic system, and if G¹And/or G³In any one be the 14th race atom (such as C or Si), then R³⁰And R³¹It is bonded on this kind of one or more G atoms, if G¹、G²And/or G³ The atom (such as N or P) of the 15th race, then R³⁰It is bonded on this kind of one or more G atoms, The most each R³⁰And R³¹It is hydrogen or C independently₁-C₁₀₀Alkyl (or C₁-C₄₀, or C₁-C₂₀Hydrocarbon Base)；

Q2 is NR¹⁷Or PR¹⁷, wherein R¹⁷Selected from containing 1-20 carbon atom (preferably 2-16, preferably 4-14, preferably 5-12, preferably 6-10 carbon atom) have 1.66 or bigger (or 1.70 Or bigger, or 1.80 or bigger, or 1.83 or bigger) the alkyl of H/C ratio, wherein It not tertiary carbon atom with the carbon atom of N or P keyed jointing, and wherein R¹⁷Can be unsubstituted or take In generation, has 1-5 substituent group, described substituent group to include F, Cl, Br, I, CF₃、NO₂, alkoxyl, Dialkyl amido, silicyl, siloxy, aryloxy group, aryl and containing 1-10 carbon Alkyl, such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, Decyl and their isomer；

Q3 is-(TT)-or-(TTT)-, the most each T is carbon or hetero atom, preferably C, O, S Or N, and described carbon or hetero atom can be unsubstituted (such as, hydrogen and described carbon or hetero atom Keyed jointing) or replace have one or more R³⁰Group, these one or more R³⁰Group and "-C-Q³=C-" Fragment forms 5-or 6-cyclic group together or includes the multi-ring of described 5-or 6-cyclic group Group；

R1 is selected from alkyl and substituted alkyl or silicyl；

R²And R¹⁰It is-E (R independently of one another¹²)(R¹³)-, wherein E is carbon, silicon or germanium, each R¹² And R¹³Independently selected from hydrogen, alkyl and substituted alkyl, alkoxyl, silicyl, amino, Aryloxy group, halogen and phosphino-, R¹²And R¹³Can engage to be formed saturated, substituted or unsubstituted Alkyl ring, wherein this ring has 4,5,6 or 7 ring carbon atoms and the wherein substituent group on this ring Can engage to form additional ring, or R¹²And R¹³Can engage to form saturated heterocyclic or full With substituted heterocycle, wherein the substituent group on this ring can engage to form additional ring；

Z is-(R₁₄)pC-C(R₁₅) q-, wherein R₁₄And R₁₅Independently selected from hydrogen, alkyl and replacement Alkyl, and the most adjacent R₁₄And R₁₅Group can engage to form aromatics or saturated, replacement Or unsubstituted alkyl ring, wherein this ring has 5,6,7 or 8 ring carbon atoms and wherein this ring On substituent group can engage to form additional ring, p is 1 or 2, and q is 1 or 2；

L is anion leaving group, and wherein this L group can be identical or different and any two L group can connect to form dianion leaving group；

N is 0,1,2,3 or 4；

L' is neutral Lewis base；With

W is 0,1,2,3 or 4；

Wherein n+w is at most 4.

H/C ratio is the ratio of hydrogen atom number and carbon atom number.Such as, methyl (C₁H₃) have 3 H/C ratio, and cyclohexyl (C₆H₁₁) group has the H/C ratio of 1.83, phenyl (C₆H₅) have 0.83 H/C ratio, myristyl phenyl (C₂₀H₃₃) have 1.65 H/C ratio.

Provide the pyridine radicals diaminourea represented by formula (I) or (II) in a still further aspect thereof Transition metal complex (is optionally used for olefinic polymerization):

Wherein:

M is the 3rd, 4,5,6,7,8,9,10,11 or 12 race's metals, the preferably the 4th race；

Each R¹Independently selected from alkyl and substituted alkyl or silicyl；

R²And R¹⁰It is-E (R independently of one another¹²)(R¹³)-, wherein E is carbon, silicon or germanium, each R¹² And R¹³Independently selected from hydrogen, alkyl and substituted alkyl, alkoxyl, silicyl, amino, Aryloxy group, halogen and phosphino-, R¹²And R¹³Can engage to be formed saturated, substituted or unsubstituted Alkyl ring, wherein this ring has 4,5,6 or 7 ring carbon atoms and the wherein substituent group on this ring Can engage to form additional ring, or R¹²And R¹³Can engage to form saturated heterocyclic or full With substituted heterocycle, wherein the substituent group on this ring can engage to form additional ring；

R17 selected from containing 1-20 carbon atom (preferably 2-16, preferably 4-14, preferably 5-12, excellent Select 6-10 carbon atom) have 1.66 or bigger (or 1.70 or bigger, or 1.80 or more The alkyl of H/C ratio greatly, or 1.83 or bigger), wherein the carbon atom with N keyed jointing is not uncle Carbon atom (preferably be secondary or primary carbon atom with the carbon atom of N keyed jointing), and wherein R¹⁷Can be not Substituted or replacement has 1-5 substituent group, described substituent group to include F, Cl, Br, I, CF₃、 NO₂, alkoxyl, dialkyl amido, silicyl, siloxy, aryloxy group, aryl and contain The alkyl of 1-10 carbon, such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, Octyl group, nonyl, decyl and their isomer；

R³、R⁴And R⁵Independently selected from hydrogen, alkyl, substituted alkyl, alkoxyl, aryloxy group, Halogen, amino and silicyl, and the most adjacent R group (R³&R⁴And/or R⁴&R⁵) can To engage to form substituted or unsubstituted alkyl or heterocycle, wherein this ring has 5,6,7 or 8 Substituent group on individual annular atoms and wherein this ring can engage to form additional ring；

R⁶、R⁷、R⁸、R⁹、R^15*And R^16*Independently selected from hydrogen, alkyl, substituted alkyl, alcoxyl Base, halogen, amino and silicyl, and the most adjacent R group (R⁶&R⁷, and/or R⁷& R^15*, and/or R^16*&R^15*, and/or R⁸&R⁹) can engage form saturated, replacement or do not take The alkyl in generation or the ring of heterocycle, wherein this ring has 5,6,7 or 8 ring carbon atoms and wherein should Substituent group on ring can engage to form additional ring；

L is anion leaving group, and wherein this L group can be identical or different and any two L group can connect to form dianion leaving group；

N is 0,1,2,3 or 4；

L' is neutral Lewis base；With

W is 0,1,2,3 or 4；

Wherein n+w is not more than 4.

In a preferred embodiment in accordance with this invention, Q¹It is via at 2 and 6 (pyridine rings On position, wherein nitrogen is 1) in carbon and Z and R²The substituted or unsubstituted pyridine connected Base.

In a preferred embodiment in accordance with this invention, G¹And G³Be each independently selected from C, N, O and S, it is preferable that there is the G of they corresponding R bases¹And G³It is methyl, ethyl, propyl group, fourth Base, amyl group, hexyl, octyl group etc., it is preferable that there is the G of they corresponding R bases¹And G³Be formed as Ring structure, preferably pyridine.

In an optional embodiment of the present invention, R¹⁷Selected from containing 1-20 carbon atom (preferably 2-16, preferably 4-14, preferably 5-12, preferably 6-10 carbon atom) have 1.66 or bigger (or Person 1.70 or bigger, or 1.80 or bigger, or 1.83 or bigger) the alkyl of H/C ratio, Wherein with N (or formula A or the Q of B²In P) carbon atom of keyed jointing is primary or secondary carbon atom, preferably Secondary carbon.

In any embodiment of the present invention, R¹⁷It is non-aromatic.

In any embodiment of the present invention, R¹⁷Ring-type (the most non-aromatic) alkyl can be selected from, Ring-type (the most non-aromatic) substituted alkyl and ring-type (the most non-aromatic) silicyl.

In any embodiment of the present invention, R¹⁷It is saturated C₅-C₁₂Cyclic group or substituted non- Aromatics C₅-C₁₂Cyclic group, preferably ring-type, the saturated alkyl containing 3-20 carbon, such as cyclopropyl, Cyclobutyl, cyclopenta, cyclohexyl, suberyl, ring octyl group, ring nonyl, ring decyl, ring 12 Alkyl or their isomer.

In any embodiment of the present invention, R¹⁷Selected from methyl, primary alkyl, branched primary alkyl, Secondary alkyl and cycloalkyl, such as methyl, ethyl, propyl group, normal-butyl, cyclohexyl, ring octyl group and Cyclo-dodecyl, condition be the carbon atom with N or P keyed jointing be primary or secondary carbon atom, preferably secondary carbon Atom.

In any embodiment of the present invention, R¹⁷It is alkyl or cyclic aliphatic hydrocarbon group.

In a preferred embodiment in accordance with this invention, Q²It is NR¹⁷。

In a preferred embodiment in accordance with this invention, Q³It is the three carbon linkers forming pyridine ring (CH-CH-CH).In another preferred embodiment, Q³It is containing a carbon and one the 15th Or 16 two atom linkers of race's element so that described linker forms five-ring heterocycles, such as miaow Azoles or substituted imidazoles.

Preferably, above-mentioned R base and other R base mentioned below contain 1-30, preferably 2-20 Individual carbon atom, particularly 6-20 carbon atom.

Preferably, M is Ti, Zr or Hf and/or E is carbon, wherein complexation based on Zr or Hf Thing is especially preferred.

In a preferred embodiment in accordance with this invention, R¹Selected from various respectively by 0-5 substituent group The substituted phenyl of sample, described substituent group includes F, Cl, Br, I, CF₃、NO₂, alkoxyl, two Alkyl amino, aryl and containing the alkyl of 1-10 carbon, such as methyl, ethyl, propyl group, butyl, Amyl group, hexyl, heptyl, octyl group, nonyl, decyl and their isomer.

In a preferred embodiment, L can be selected from halogen, alkyl, aryl, alkoxyl, Amino, hydrogen-based (hydrido), phenoxy group, hydroxyl, silicyl, pi-allyl, thiazolinyl and alkynes Base.The selection of leaving group is depended on obtaining synthetic route that complex taked and can pass through The addition reaction being adapted in polymerization activation method after a while changes.Such as, when using noncoordinating the moon When ion such as four (pentafluorophenyl group)-boric acid N, N-dimethyl puratized agricultural spray or three (pentafluorophenyl group) borine, Preferably L is alkyl.In another embodiment, two L groups can connect to be formed double Anion leaving group, such as oxalate.

In another embodiment, each L' independently selected from ether, thioether, amine, nitrile, imines, Pyridine and phosphine, preferably ether.

Preferably R²Base and preferred R¹⁰Base includes CH₂、CMe₂、SiMe₂、SiEt₂、SiPr₂、 SiBu₂、SiPh₂, Si (aryl)₂, Si (alkyl)₂, CH (aryl), CH (Ph), CH (alkyl) With CH (2-isopropyl phenyl).

R²And R¹⁰The preferably pairing of group (is expressed as R²&R¹⁰) including: (CH₂&CH(Ph))、 (CMe₂With CH (Ph)), (CH₂With CH (aryl)), (CH₂With CH (alkyl)), wherein alkyl It is C₁-C₄₀Alkyl (preferably C₁-C₂₀Alkyl, preferably methyl, ethyl, propyl group, butyl, amyl group, Hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl and their isomer In one or more), aryl is C₅-C₄₀Aryl (preferably C₆-C₂₀Aryl, preferably phenyl or replacement Phenyl, preferably phenyl, 2-isopropyl phenyl or 2-tert-butyl-phenyl).

In another embodiment, R²It is CH₂Or CMe₂, R¹⁰Selected from CH (Ph), CH (aryl) With CH (alkyl), wherein alkyl is C₁-C₄₀Alkyl (preferably C₁-C₂₀Alkyl, preferably methyl, ethyl, Propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, 12 One or more in alkyl and their isomer), aryl is C₅-C₄₀Aryl (preferably C₆-C₂₀ Aryl, preferably phenyl or substituted phenyl, preferably phenyl, 2-isopropyl phenyl or 2-tert-butyl benzene Base).

In any embodiment described herein, E is preferably carbon.

In any embodiment described herein, R²Represented by with following formula:

Wherein R¹²" it is hydrogen, alkyl, aryl or halogen；R¹³" it is hydrogen, alkyl, aryl or halogen, Preferably R¹²" and R¹³" identical.

In any embodiment described here, R⁶, R⁷, R⁸, R⁹, R^15*And R^16*Can be independent Ground is selected from hydrogen, alkyl, substituted alkyl, alkoxyl, halogen, amino and silicyl.

In any embodiment described herein, R¹、R³、R⁴And R⁵Can each contain 1-30 Individual carbon atom, preferably R¹、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁵And R¹⁶Each containing 1-30 Individual carbon atom.

In any embodiment described herein, E is carbon and R¹Have 0 selected from replacement, 1,2,3, The phenyl of 4 or 5 substituent groups, described substituent group is selected from F, Cl, Br, I, CF₃、NO₂, alkane Epoxide, dialkyl amido, alkyl and substituted alkyl, it contains 1-10 carbon.

In a preferred embodiment, pyridine radicals diaminourea transition metal complex is by above-mentioned Formula (A) or (B) represent, M is group-4 metal, preferably Zr or Hf, preferably Hf.

In a preferred embodiment, pyridine radicals diaminourea transition metal complex is by above-mentioned Formula (I) or (II) represent, M is group-4 metal, preferably Zr or Hf, preferably Hf.

In a preferred embodiment, pyridine radicals diaminourea transition metal complex is by above-mentioned formula (A), (B), (I) or (II) represent, and at described R¹⁰In group, R¹²And R¹³It is H and R¹ Being 2 containing 12-20 (preferably 12-15) individual carbon, the dibasic phenyl of 6-, M is that group-4 metal is (excellent Select Zr or Hf, preferably Hf), E is carbon, at R²In group, R¹²It is H and R¹³Preferably containing 6-20 The alkyl of individual carbon, R¹⁷It is containing 1-20 carbon the group with 1.66 or higher H/C ratios.

In a preferred embodiment, pyridine radicals diaminourea transition metal complex is by above-mentioned formula (A), (B), (I) or (II) represent, R²R in group¹²And R¹³It is all C₁-C₁₀₀Alkyl is (preferably C₆-C₄₀Alkyl, preferably C₆-C₃₀Alkyl, or C₁-C₁₂Alkyl, or C₁-C₆Alkyl, or first Base, ethyl, propyl group, butyl, amyl group, hexyl, octyl group, nonyl, decyl or their isomery Body).

In a preferred embodiment, pyridine radicals diaminourea transition metal complex is by above-mentioned formula (A), (B), (I) or (II) represent, and at R²In group, R¹²It is H, R¹³It is (excellent containing 1-100 Select 6-40, preferably 6-30) group of individual carbon, M be group-4 metal (preferably Zr or Hf, preferably Hf), E is carbon, at R¹⁰In base, R¹²With R¹³Identical and preferably hydrogen or methyl；R¹⁷It is containing 1-20 Individual carbon also has the group of 1.66 or higher H/C ratios.

In the second aspect of the invention, it is provided that synthesize the various sides of complex described herein Method.

Part synthesizes

Pyridine radicals two amine ligand described herein is typically prepared by multiple steps.One step includes system Standby containing amine " bridging agent " group, wherein said bridging agent is typically aryl methyl amine or substituted The borate of amine.This can be prepared in two stages by aryl-methyl boron acid esters containing amine bridging agent, First include by non-reactive solvent (such as, CCl₄, benzene) in free radical halogenation by methyl Change into halogen-methyl.Second step then includes making this Halogen-methyl species and amine or shielded amine Or the protected amine of deprotonation reacts to produce the bridging agent Han amine.Then make this containing amine bridging agent With applicable containing pyridine material, such as 6-bromo-2-pyridyl formaldehyde coupling.This coupling step typical case Ground uses metallic catalyst (such as, Pd (PPh by less than 5mol% useful load₃)₄).Even at this After connection step, then make to be described as the described new derivatives of amine-bridging agent-pyridine-aldehyde With diamine reactant to prepare imine derivative amine-bridging agent-pyridine-imines in the condensation reaction. The aryl anion, alkyl anion or the hydride ion source that may then pass through and be suitable for are reacted it It is reduced to pyridine radicals two amine ligand.When using aryl lithium or lithium alkylide reaction reagent, this reaction Typically carry out at a temperature of-100 DEG C to 50 DEG C in ether solvents.When using sodium cyanoborohydride Time, in methanol, typically carry out this reaction under reflux.Column chromatography can be used or by including The program of formation ackd salt is the product purification Han amine, such as US by pyridine radicals diamidogen product and intermediate Described in embodiment 2 in 8,212,047B2 like that.

Typical protonolysis and methylation reaction can be used to realize pyridine radicals diaminourea metal network Compound is by the preparation of pyridine radicals diamidogen.In protonolysis reacts, make described pyridine radicals diamidogen with suitable The metal reactant closed reacts to produce pyridine radicals diaminourea metal complex.The metal reaction being suitable for Thing will be with alkalescence leaving group, and described alkalescence leaving group will accept proton from pyridine radicals diamidogen, Then typically leave from product and be removed.The metal reactant being suitable for includes, but are not limited to HfBn₄(Bn=CH₂Ph)、ZrBn₄、TiBn₄、ZrBn₂Cl₂(OEt₂)、HfBn₂Cl₂(OEt₂)₂、 Zr(NMe₂)₂Cl₂(dimethoxy-ethane), Hf (NMe₂)₂Cl₂(dimethoxy-ethane), Hf(NMe₂)₄With Hf (NEt₂)₄.Can be by inciting somebody to action with suitable organometallic reaction reagent reacting Containing metal-chloro, the pyridine radicals diamino of the PDA dichloride complex in flow process 1 such as below Base (PDA) metal complex alkylation.The reaction reagent being suitable for includes organolithium and organic-magnesium, and Grignard reagent.Described alkylation typically in ether or hydrocarbon solvent or solvent mixture typically Carry out at a temperature of-100 DEG C to 50 DEG C.

Flow process 1

Wherein in flow process 1, R, R¹、R²And R³Independently selected from H, alkyl (such as alkyl,

Aryl), substituted hydrocarbon radical (such as heteroaryl) and silicyl, Rn indicated hydrogen, alkyl or replace hydrocarbon Base, they can engage to form polycyclic aromatic ring, and n is 1,2,3 or 4；R⁴Selected from C₁-C₂₀ Non-aromatic hydrocarbon group, preferably cyclic group.

Another route of pyridine radicals diaminourea complex (pyridyldiamide complex) is to use At least two equivalent alkali, such as butyl lithium is by pyridine radicals diamidogen deprotonation, to form two lithium pyridine radicals Diaminourea material.Then this lithium salts and metal halide, such as HfCl can be made₄Or ZrCl₄ Reaction, forms pyridine radicals diaminourea complex.

The R of pyridine radicals diaminourea complex¹⁷The selection meeting of the group polymerization activity to activated complex With the performance of prepared polymer, there is big impact.Especially, R¹⁷The cyclohexyl of position (with Phenyl is contrary) have been found that catalyst activity is significantly increased for propylene polymerization.Additionally, it is made For standby polyacrylic fusing point catalyst substituted for cyclohexyl much higher.It is not intended to be subject to Theoretical constraint, inventor advises at R¹⁷It is favourable for using non-aromatic hydrocarbon group in position, because These groups improve the confession ability of immigrants of they keyed jointings amino nitrogen thereon.Than phenyl, more there is power supply Other group of sub-property can also be desirable to, such as methyl, ethyl, propyl group, primary alkyl, Change primary alkyl, secondary alkyl, cycloalkyl and tertiary alkyl.

Activity is described as the polymer/mmol prepared by kg from pyridine radicals diaminourea complex Transition metal/hour.For the propylene polymerization carried out at 70 DEG C, at R¹⁷Cyclohexyl is used at group Replace produce can form polyacrylic catalyst with the activity more than 300kg/mmol/hr, And wherein R¹⁷It it is the activity of the catalyst performance 91kg/mmol/hr of phenyl.For at 85 DEG C The propylene polymerization carried out, at R¹⁷Producing with the replacement of cyclohexyl at group can be with more than 300 The activity of kg/mmol/hr forms polyacrylic catalyst, and wherein R¹⁷It it is the catalyst table of phenyl The activity of existing 100kg/mmol/hr.For the propylene polymerization carried out at 100 DEG C, at R¹⁷Base Produce can form polypropylene with the activity more than 110kg/mmol/hr with replacing of cyclohexyl at Tuan Catalyst, and wherein R¹⁷It is that the catalyst performance of phenyl is less than the activity of 70kg/mmol/hr.

The invention still further relates to use catalyst described herein to prepare polyolefin, the most polyacrylic side Method, the condition that wherein said catalyst describes for using the test 1-3 in embodiment at 70 DEG C The propylene polymerization carried out has 200kg polymer/mmol catalyst/h or bigger, preferably 200kg The activity of polymer/mmol catalyst/h or bigger.

The invention further relates to the preparation method of above-mentioned complex, the intermediate of above-mentioned complex The method that preparation method and the above-mentioned complex of use make olefinic polymerization, wherein said complex is for making The propylene polymerization carried out at 70 DEG C by condition described in the test 1-3 in embodiment has 200kg Polymer/mmol catalyst/h or bigger, preferably 200kg polymer/mmol catalyst/h or Bigger activity.

Activator

After having synthesized complex, can by by them with activator by being known from literature that Any mode combines formation catalyst system, including poly-for slurry or gas phase by loading them Close.Catalyst system can also add or result from polymerisation in solution or polymerisation in bulk (in monomer) to. Catalyst system generally comprises above-mentioned complex and activator such as aikyiaiurnirsoxan beta or non-coordinating anion. Aluminoxanes solution can be used, including MAO (referred to as MAO) and containing some senior alkyls Activate with the deliquescent modified MAO (referred to herein as MMAO) of improvement.The MAO being particularly useful can To buy with the 10wt% solution in toluene from Albemarle.The catalyst used in the present invention System is preferably used selected from aikyiaiurnirsoxan beta, such as MAO, modified methylaluminoxane, aluminium ethide The activator of oxygen alkane, isobutyl aluminium alkoxide etc..

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

Noncoordinating the moon of type described in EP 277003 A1 and EP 277004 A1 can also be used Ion (referred to as NCA) activates.NCA can add in ion pair form, uses such as, [DMAH]⁺[NCA]^-, in wherein N, N-dimethyl puratized agricultural spray (DMAH) cation and transition metal complex The reaction of alkaline leaving group and form transition metal complex cation and [NCA]^-.In precursor Cation can also be trityl.Or, transition metal complex can with neutral NCA precursor, Such as B (C₆F₅)₃Reaction, it extracts anionic group from complex and forms activating substance.Useful Activator include four (pentafluorophenyl group) boric acid N, N-dimethyl puratized agricultural spray (that is, [PhNMe₂H]B(C₆F₅)₄) With four (seven fluoronaphthalene bases) boric acid N, N-dimethyl puratized agricultural spray, wherein Ph is phenyl, and Me is methyl.

Additionally, the most useful preferred activator includes US 7, the 169th hurdle in 247,687 50 walk to the 174th hurdle the 43rd row, and the especially the 172nd hurdle the 24th walks to the 173rd hurdle the 53rd row Those described.

When using NCA (such as ion or neutral stoichiometric activator), complex and activator Mol ratio is typically 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 and 1:1-1:1.2.

Or, conactivator can be used in catalyst system here.Complex and-common work Agent mol 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 and 1:10-2:1。

Term " non-coordinating anion " (NCA) refers to be unworthy of being positioned at described cation or only weakly joining It is positioned at described cation, thus keeps enough unstable with the anion replaced by neutral Lewis base. " compatibility " non-coordinating anion is non-degradable for neutral when the complex being initially formed decomposes Those.Additionally, anion substituent or fragment are not transferred to cation by this anion, make its shape Become neutral transition metal compound and the neutral by-product from this anion.Can make according to the present invention Non-coordinating anion be such anion, they are compatible, its ionic charge are being put down Stablize transition-metal cation in the sense that weighing apparatus+1, still keep enough unstability to allow to exist In polymerization process replaced.

Use neutrality or the ionizing of ion-type or Stoichiometric activators within the scope of the invention, Such as four (pentafluorophenyl group) boric acid three (normal-butyl) ammonium, three (perfluorophenyl) boron metalloid precursor or three (perfluoronapthyl) boron metalloid precursor, the miscellaneous borane anion of many halogenations (WO 98/43983), boric acid is (beautiful State's patent No. 5,942,459) or combinations thereof.It is used alone neutrality or ion activation agent or and aluminum Oxygen alkane or modified alumoxane activators are used in combination the most within the scope of the present invention.

The example of neutral stoichiometric activator include trisubstituted boron, tellurium, aluminum, gallium and indium or it Mixture.Described three substituent groups are each independently selected from alkyl, thiazolinyl, halogen, replace Alkyl, aryl, aryl halide, alkoxyl and halogen (halide).Preferably, described three groups Independently selected from halogen, single or multiple ring (including that halogen is substituted) aryl, alkyl and alkenyl compound, With their mixture, preferably contain the thiazolinyl of 1-20 carbon atom, containing 1-20 carbon atom Alkyl, alkoxyl containing 1-20 carbon atom and the aryl containing 3-20 carbon atom (include taking The aryl in generation).It is further preferred that these three group is the alkyl containing 1-4 carbon, phenyl, naphthyl or Their mixture.Even further preferably, described three groups are halogenation, it is preferably fluorination, Aryl.Preferably neutral stoichiometric activator is three (perfluorophenyl) boron or three (perfluoronapthyl) Boron.

Ionic stoichiometric activator compound can comprise active proton, or certain other with The residual ion of ionized compound associates, but is not coordinated with it, or only loose with it The cation of coordination.Such compound and the like is described in European Published text EP 0 570 982 A；EP 0 520 732 A；EP 0 495 375 A；EP 0 500 944 B1；EP 0 277 003 A；EP 0 277 004 A；U.S. Patent number 5,153,157；5,198,401；5,066,741； 5,206,197；5,241,025；5,384,299；On August 3rd, 5,502,124 and 1994 The U.S. Patent Application Serial Number 08/285 submitted to, in 380, all these documents are by with reference to completely It is expressly incorporated herein.

Can be used as the preferred compound of activator in the methods of the invention and include cation and compatible Non-coordinating anion, described cation is preferably capable of protogenic Bronsted acid, described the moon Ion is relatively large (bulky), it is possible to stable when the two compound combines time institute Formed active catalyst species (the 4th race's cation), and described anion will be enough shakiness Fixed with by olefinic, diolefins and acetylene series unsaturation substrate or other neutral Lewis base such as ether, Amine and analog substitute.The useful compatible non-coordinating anion of two classes is at EP 0 277,003 A1 Being disclosed with in EP 0 277,004 A1: 1) anion that comprises multiple lipophilic group joins Position complex, this lipophilic group and the charged metal in center or metalloid core are covalently This core is also shielded by coordination, and 2) comprise the anion such as carborane of multiple boron atom, metal carbon Borine and borine.

In a preferred embodiment, Stoichiometric activators includes cation and anion group Point, and preferably represented by below general formula (II):

(Z)_d ⁺(A^d-) (II)

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

When Z is that (L-H) is so that cationic components is (L-H)_d ⁺Time, cationic components can include Blang Si Taide acid, such as, enable to the bulky ligand metallocene of self-contained transition-metal catalyst precursor The protonated Lewis base of structure division such as alkyl or aryl protonation, thus obtain cation Transition metal material.Preferably, reactivity cation (L-H)_d ⁺Can be Bronsted acid, its Can be that transition metal-catalyzed precursor supplies proton, thus produce transition-metal cation, including ammonium, OxygenPhosphorusMonosilaneAnd their mixture, preferably methylamine, aniline, dimethylamine, Diethylamine, methylphenylamine, diphenylamines, trimethylamine, triethylamine, DMA, first Base diphenylamine, pyridine, to bromine DMA, to nitro-DMA Ammonium；Derive from the phosphorus of triethyl phosphine, triphenylphosphine and diphenylphosphineDerive from ether such as dimethyl Ether, Anaesthetie Ether, oxolane and twoThe oxygen of alkaneDerive from thioether, such as diethyl thioether With the sulfonium of Tetramethylene sulfide, and their mixture.

When Z is reducible lewis acid, it is preferably by formula (Ar3C⁺) represent, wherein Ar It is aryl or replacement has heteroatomic aryl, C₁-C₄₀Alkyl or substituted C₁-C₄₀Alkyl, preferably institute State reducible lewis acid by formula (Ph₃C⁺) represent, wherein Ph is phenyl or replacement has heteroatomic Phenyl, C₁-C₄₀Alkyl or substituted C₁-C₄₀Alkyl.In a preferred embodiment, described Reducible lewis acid is triphenylcarbenium

Anionic group A^d-Including having formula [M^k+Q_n]^d-Those, wherein k is 1,2 or 3； N is 1,2,3,4,5 or 6, preferably 3,4,5 or 6；N-k=d；M is selected from element week The element of phase Biao 13 race, preferably boron or aluminum, Q is hydrogen-based (hydride), bridging independently Or the dialkyl amido (amido) of non-bridging, halogen, alkoxyl (alkoxide), aryloxy group (aryloxide), alkyl, substituted alkyl, halocarbyl (halocarbyl), substituted halogen For carbon back and the alkyl of halogen substiuted, described Q contains at most 20 carbon atoms, condition be in Q extremely There is a halogen more, and 2 Q bases can form ring structure.Preferably, each Q is to contain The fluorination alkyl of 1-20 carbon atom, the most each Q is fluoro aryl, the most each Q It is five fluorinated aryls.The A being suitable for^dThe example of-component also includes such as U.S. Patent number 5,447,895 Disclosed in two boron compounds, the document is hereby incorporated by reference herein.

In a preferred embodiment, the present invention relates to make the method for olefinic polymerization, including making Alkene (optimal ethylene and/or propylene) and described catalyst compounds and the boracic represented by formula (14) NCA activating agent:

Z_d ⁺(A^d-) (14)

Wherein: Z is (L-H) or reducible lewis acid；L is that neutral Lewis base is (as above Further describe)；H is hydrogen；(L-H) it is Bronsted acid (as further described above)；A^d- It it is the boracic non-coordinating anion (as further described above) with electric charge d-；D is 1,2 or 3.

In a preferred embodiment, in any NCA represented by above-mentioned formula 14, described Reducible lewis acid is by formula (Ar₃C⁺) represent, wherein Ar is aryl or replacement has heteroatomic virtue Base, C₁-C₄₀Alkyl or substituted C₁-C₄₀Alkyl, the most described reducible lewis acid is by formula (Ph₃C⁺) represent, wherein Ph is phenyl or replacement has heteroatomic phenyl, C₁-C₄₀Alkyl or replacement C₁-C₄₀Alkyl.

In a preferred embodiment, in any NCA represented by above-mentioned formula 14, Z_d ⁺ By formula: (L-H)_d ⁺Representing, wherein L is neutral Lewis base；H is hydrogen；(L-H) it is cloth Lanace platform Moral acid；It is 1,2 or 3 with d, preferably (L-H)_d ⁺It is selected from ammonium, oxygenPhosphorusMonosilaneWith The Bronsted acid of their mixture.

In a preferred embodiment, in any NCA represented by above-mentioned formula 14, cloudy from Subgroup divides A^d-By formula [M^*k^*+Q^*n*]d^*-represent, wherein k^*It is 1,2 or 3；N* is 1,2,3, 4,5 or 6 (preferably 1,2,3 or 4)；n^*-k^*=d^*；M^*It is boron；And Q^*Independently selected from hydrogen Base, bridging or non-bridging dialkyl amido (amido), halogen, alkoxyl, aryloxy group, alkyl, Substituted alkyl, halocarbyl, substituted halocarbyl and the substituted alkyl of halogen, described Q^*Containing extremely Many 20 carbon atoms, condition is Q^*In a halogen at most occurs.

The invention still further relates to make the method for olefinic polymerization, including making alkene (such as ethylene and/or propylene) With described catalyst compounds and the NCA activating agent that represented by formula (I):

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

Wherein R is single anion ligand；M^**It is the 13rd race's metal or metalloid；ArNHal is halogen Change, nitrogenous aromatic ring, polycyclic aromatic ring, or two of which or more ring (or fused ring system) that This or the aromatic ring group being jointly directly connected to；It is 0,1,2 or 3 with n.Generally, containing Formulas I The NCA of anion also comprises the ionic catalysis being not substantially affected by being formed with described transistion metal compound The cation being suitable for of agent complex interference, the most described cation is above-mentioned Z_d ⁺。

In a preferred embodiment, any of the anion that represented by above-mentioned Formulas I is being comprised In NCA, R is selected from substituted or unsubstituted C₁-C₃₀Hydrocarbon-based aliphatic or aromatic group, wherein replacement is Refer to that at least one hydrogen on carbon atom is by following replacement: alkyl, halogen, halocarbyl, alkyl or The substituted organic quasi-metal of halocarbyl, dialkyl amido, alkoxyl, aryloxy group, alkyl sulfenyl (alkylsulfido), artyl sulfo (arylsulfido), alkyl phosphorio (alkylphosphide) Aryl phosphorio (arylphosphide) or other anion substituent；Fluorine-based (fluoride)；Volume Big alkoxyl, wherein volume refers to greatly C₄-C₂₀Alkyl；-SR1、-NR² ₂With-PR³ ₂, the most often Individual R¹、R²Or R³It is above-mentioned substituted or unsubstituted alkyl independently；Or C₁-C₃₀Alkyl is substituted to be had Machine metalloid.

In a preferred embodiment, any of the anion that represented by above-mentioned Formulas I is being comprised In NCA, NCA also comprises containing by formula (Ar₃C⁺) the reducible lewis acidic cation that represents, wherein Ar is aryl or replacement has heteroatomic aryl, C₁-C₄₀Alkyl or substituted C₁-C₄₀Alkyl, preferably Described reducible lewis acid is by formula (Ph₃C⁺) represent, wherein Ph is phenyl or replacement has hetero atom Phenyl, C₁-C₄₀Alkyl or substituted C₁-C₄₀Alkyl.

In a preferred embodiment, at any NCA containing the anion represented by above-mentioned Formulas I In, NCA also comprises by formula (L-H)_d ⁺The cation represented, wherein L is neutral Lewis base；H is Hydrogen；(L-H) it is Bronsted acid；It is 1,2 or 3 with d, preferably (L-H)_d ⁺Be selected from ammonium, OxygenPhosphorusMonosilaneBronsted acid with their mixture.

Other example of useful activator includes U.S. Patent number 7,297,653 and 7,799,879 Disclosed in those.

The most useful another kind of activator comprises the cation oxidant represented by formula (16) and non-joins Position, the salt of compatible anionic:

(OX^e+)_d(A^d-)_e (16)

Wherein OX^e+It it is the cation oxidant with electric charge e+；E is 1,2 or 3；D is 1,2 Or 3；A^d-It it is the non-coordinating anion (as further described above) with electric charge d-.Cation oxygen The example of agent includes: ferroceneThe substituted ferrocene of alkylAg⁺Or Pb⁺²。A^d-Excellent The embodiment of choosing includes four (pentafluorophenyl group) borate.

In another embodiment, catalyst compounds can make together with the activator of large volume With." large volume activator " used herein above refers to anion active agent expressed by the following formula:

Wherein:

Each R₁It is halogen (halide) independently, the most fluorine-based；

Each R₂It is halogen, C independently₆-C₂₀Substituted aromatic hydrocarbyl or formula O-Si-R_aFirst Silane epoxide, wherein R_aIt is C₁-C₂₀Alkyl or hy drocarbylsilyl (preferably R₂It it is fluorine-based or perfluor Change phenyl)；

Each R₃It is halogen, C₆-C₂₀Substituted aromatic hydrocarbyl or formula O-Si-R_aMonosilane oxygen Base, wherein R_aIt is C₁-C₂₀Alkyl or hy drocarbylsilyl (preferably, R₃It is fluorine-based or C₆Perfluorinate Aromatic hydrocarbyl)；Wherein R₂And R₃One or more saturated or unsaturated, replacement can be formed Or unsubstituted ring (preferably R₂And R₃Form fluoridized benzyl ring)；

L is neutral Lewis base；

(L-H)⁺It it is Bronsted acid；

D is 1,2 or 3；

Wherein said anion has the molecular weight more than 1020g/mol；With

Wherein at least three in the substituted radical on B atom each has and is more than Or it is more thanOr it is more thanMolecular volume.

" molecular volume " is used as the space multistory volume of the activator molecule being in solution at this Approximation.The contrast of the substituent group with different molecular volume allows to think have less molecule The substituent group of volume is " less large volume " compared with the substituent group with relatively macromole volume. On the contrary, it is believed that have compared with the substituent group of macromole volume with there is less molecular volume It is " more large volume " that substituent group is compared.

Molecular volume can be such as " A Simple'Back of the Envelope'Method for Estimating the Densities and Molecular Volumes of Liquids And Solids ", Journal of Chemical Education, Vol.71, No.11, In November, 1994, pp.962-964 reports and calculates like that.(unit is molecular volume (MV)) use formula: MV=8.3Vs to calculate, wherein Vs is scale volume.Vs is to constitute The relative volume sum of atom, and used the relative volume of following table to calculate by the molecular formula of substituent group. For condensed ring, Vs reduces by 7.5%/condensed ring.

Element	Relative volume
		H	1
1stThe short cycle, Li-F	2
		2ndThe short cycle, Na-Cl	4
1stLong period, K-Br	5
		2ndLong period, Rb-I	7.5
3rdLong period, Cs-Bi	9

The exemplary bulky substituent of the activator being suitable for here and they corresponding scale volumes It is shown in following table with molecular volume.Dotted line key instruction and boron keyed jointing, as in formula above.

The exemplary large volume activator that can be used for catalyst system includes: four (perfluoronapthyl) boron Acid trimethyl ammonium, four (perfluoronapthyl) boric acid triethyl ammonium, four (perfluoronapthyl) boric acid tripropyl ammonium, Four (perfluoronapthyl) boric acid three (normal-butyl) ammonium, four (perfluoronapthyl) boric acid three (tert-butyl group) ammonium, four (perfluoronapthyl) boric acid N, N-dimethyl puratized agricultural spray, four (perfluoronapthyl) boric acid N, N-diethyl puratized agricultural spray, Four (perfluoronapthyl) boric acid N, N-dimethyl-(2,4,6-trimethyl puratized agricultural spray), four (perfluoronapthyl) boron Acid(tropillium), four (perfluoronapthyl) borateFour (perfluoronapthyl) boron Triphenyl phosphate base phosphorusFour (perfluoronapthyl) boric acid triethyl-silicaneFour (perfluoronapthyl) boric acid Benzene (diazonium), four (perfluorinated biphenyl) boric acid trimethyl ammonium, four (perfluorinated biphenyl) boron triethylenetetraminehexaacetic acid Base ammonium, four (perfluorinated biphenyl) boric acid tripropyl ammonium, four (perfluorinated biphenyl) boric acid three (normal-butyl) Ammonium, four (perfluorinated biphenyl) boric acid three (tert-butyl group) ammonium, four (perfluorinated biphenyl) boric acid N, N-diformazan Base puratized agricultural spray, four (perfluorinated biphenyl) boric acid N, N-diethyl puratized agricultural spray, four (perfluorinated biphenyl) boric acid N, N-dimethyl-(2,4,6-trimethyl puratized agricultural spray), four (perfluorinated biphenyl) boric acidFour (perfluors Xenyl) borateFour (perfluorinated biphenyl) boric acid triphenyl phosphorusFour (perfluor connection Phenyl) boric acid triethyl-silicaneFour (perfluorinated biphenyl) boric acid benzene (diazonium), [the tertiary fourth of 4- Base-PhNMe₂H][(C₆F₃(C₆F₅)₂)₄B] and U.S. Patent number 7,297,653 disclosed in class Type.

Can serve as the exemplary of activator in the inventive method, but nonrestrictive example be: Four (perfluorophenyl) boric acid N, N-dimethyl puratized agricultural spray；Four (perfluorophenyl) boric acid methyl two (octadecane Base) ammonium；Four (perfluorophenyl) boric acid methyl two (C_14-20Alkyl) ammonium；Tetraphenylboronic acid trimethyl ammonium, Tetraphenylboronic acid triethyl ammonium, tetraphenylboronic acid tripropyl ammonium, tetraphenylboronic acid three (normal-butyl) ammonium, Tetraphenylboronic acid three (tert-butyl group) ammonium, tetraphenylboronic acid N, N-dimethyl puratized agricultural spray, tetraphenylboronic acid N, N-diethyl puratized agricultural spray, tetraphenylboronic acid N, N-dimethyl-(2,4,6-trimethyl puratized agricultural spray), four benzene Ylboronic acidTetraphenylboronic acid triphenylcarbeniumTetraphenylboronic acid triphenyl phosphorusTetraphenyl Boric acid triethyl-silicaneTetraphenylboronic acid benzene (diazonium), four (pentafluorophenyl group) boric acid front three Base ammonium, four (pentafluorophenyl group) boric acid triethyl ammonium, four (pentafluorophenyl group) boric acid tripropyl ammonium, four (five Fluorophenyl) boric acid three (normal-butyl) ammonium, four (pentafluorophenyl group) boric acid three (sec-butyl) ammonium, four (five fluorine Phenyl) boric acid N, N-dimethyl puratized agricultural spray, four (pentafluorophenyl group) boric acid N, N-diethyl puratized agricultural spray, four (five Fluorophenyl) boric acid N, N-dimethyl-(2,4,6-trimethyl puratized agricultural spray), four (pentafluorophenyl group) boric acid Four (pentafluorophenyl group) borateFour (pentafluorophenyl group) boric acid triphenyl phosphorusFour (five fluorine Phenyl) boric acid triethyl-silicaneFour (pentafluorophenyl group) boric acid benzene (diazonium), four (2,3,4,6- Tetrafluoro phenyl) boric acid trimethyl ammonium, four (2,3,4,6-tetrafluoro phenyl) boric acid triethyl ammonium, four (2,3,4,6-tetrafluoro phenyl) boric acid tripropyl ammonium, four (2,3,4,6-tetrafluoro phenyl) boric acid three (positive fourth Base) ammonium, four (2,3,4,6-tetrafluoro phenyl) boric acid dimethyl (tert-butyl group) ammonium, four (2,3,4,6-tetra- Fluorophenyl) boric acid N, N-dimethyl puratized agricultural spray, four (2,3,4,6-tetrafluoro phenyl) boric acid N, N-diethyl Puratized agricultural spray, four (2,3,4,6-tetrafluoro phenyl) boric acid N, N-dimethyl-(2,4,6-trimethyl puratized agricultural spray), Four (2,3,4,6-tetrafluoro phenyl) boric acidFour (2,3,4,6-tetrafluoro phenyl) borateFour (2,3,4,6-tetrafluoro phenyl) boric acid triphenyl phosphorusFour (2,3,4,6-tetrafluoro phenyl) boron Triethylenetetraminehexaacetic acid base monosilaneFour (2,3,4,6-tetrafluoro phenyl) boric acid benzene (diazonium), four (perfluor naphthalenes Base) boric acid trimethyl ammonium, four (perfluoronapthyl) boric acid triethyl ammonium, four (perfluoronapthyl) boric acid 3 third Base ammonium, four (perfluoronapthyl) boric acid three (normal-butyl) ammonium, four (perfluoronapthyl) boric acid three (tert-butyl group) Ammonium, four (perfluoronapthyl) boric acid N, N-dimethyl puratized agricultural spray, four (perfluoronapthyl) boric acid N, N-diethyl Puratized agricultural spray, four (perfluoronapthyl) boric acid N, N-dimethyl-(2,4,6-trimethyl puratized agricultural spray), four (perfluor naphthalenes Base) boric acidFour (perfluoronapthyl) borateFour (perfluoronapthyl) boric acid triphenyl PhosphorusFour (perfluoronapthyl) boric acid triethyl-silicaneFour (perfluoronapthyl) boric acid benzene (diazonium), four (perfluorinated biphenyl) boric acid trimethyl ammonium, four (perfluorinated biphenyl) boric acid triethyl ammonium, four (perfluorinated biphenyl) boric acid tripropyl ammonium, four (perfluorinated biphenyl) boric acid three (normal-butyl) ammonium, four (complete Fluorine xenyl) boric acid three (tert-butyl group) ammonium, four (perfluorinated biphenyl) boric acid N, N-dimethyl puratized agricultural spray, Four (perfluorinated biphenyl) boric acid N, N-diethyl puratized agricultural spray, four (perfluorinated biphenyl) boric acid N, N-dimethyl -(2,4,6-trimethyl puratized agricultural spray), four (perfluorinated biphenyl) boric acidFour (perfluorinated biphenyl) boric acid TriphenylcarbeniumFour (perfluorinated biphenyl) boric acid triphenyl phosphorusFour (perfluorinated biphenyl) boric acid three Ethyl silicaneFour (perfluorinated biphenyl) boric acid benzene (diazonium), four (3,5-double (trifluoromethyls) Phenyl) boric acid trimethyl ammonium, four (3,5-double (trifluoromethyl) phenyl) boric acid triethyl ammonium, four (3,5- Double (trifluoromethyl) phenyl) boric acid tripropyl ammonium, four (3,5-double (trifluoromethyl) phenyl) boric acid three (normal-butyl) ammonium, four (double (trifluoromethyl) phenyl of 3,5-) boric acid three (tert-butyl group) ammonium, four (3,5- Double (trifluoromethyl) phenyl) boric acid N, N-dimethyl puratized agricultural spray, four (3,5-double (trifluoromethyl) phenyl) Boric acid N, N-diethyl puratized agricultural spray, four (double (trifluoromethyl) phenyl of 3,5-) boric acid N, N-dimethyl -(2,4,6-trimethyl puratized agricultural spray), four (double (trifluoromethyl) phenyl of 3,5-) boric acidFour (3,5- Double (trifluoromethyl) phenyl) borateFour (double (trifluoromethyl) phenyl of 3,5-) boric acid three Phenyl phosphorusFour (double (trifluoromethyl) phenyl of 3,5-) boric acid triethyl-silicaneFour (3,5-is double (trifluoromethyl) phenyl) boric acid benzene (diazonium) and dialkyl ammonium salt, such as: four (pentafluorophenyl group) boron Acid two (isopropyl) ammoniums and four (pentafluorophenyl group) boric acid dicyclohexyl ammonium；With additional three-substituted phosphorusSalt, such as four (pentafluorophenyl group) boric acid three (o-tolyl) phosphorusWith four (pentafluorophenyl group) boric acid three (2,6-3,5-dimethylphenyl) phosphorus

Preferably activator includes four (perfluoronapthyl) boric acid N, N-dimethyl puratized agricultural spray, four (perfluor connection Phenyl) boric acid N, N-dimethyl puratized agricultural spray, four (3,5-double (trifluoromethyl) phenyl) boric acid N, N-diformazan Base puratized agricultural spray, four (perfluoronapthyl) borateFour (perfluorinated biphenyl) borateFour (double (trifluoromethyl) phenyl of 3,5-) borateFour (perfluorophenyl) boric acid three Phenyl carbons[Ph₃C⁺][B(C₆F₅)₄ ^-],[Me₃NH⁺][B(C₆F₅)₄-]；1-(4-(three (five fluorine Phenyl) boric acid)-2,3,5,6-tetrafluoro phenyl) pyrrolidineWith four (pentafluorophenyl group) borate, 4-(three (pentafluorophenyl group) boric acid)-2,3,5,6-ptfe pyridine.

In a preferred embodiment, activator comprises triaryl carbon(such as tetraphenyl boron Triphenyl phosphate base carbonFour (pentafluorophenyl group) borateFour (2,3,4,6-tetrafluoro phenyl) BorateFour (perfluoronapthyl) borateFour (perfluorinated biphenyl) boric acid TriphenylcarbeniumFour (double (trifluoromethyl) phenyl of 3,5-) borate)。

In another embodiment, one or more during activator comprises following material: four (five Fluorophenyl) boric ammonium, four (pentafluorophenyl group) boric acid N, N-dialkyl group puratized agricultural spray, four (phenyl-pentafluorides Base) boric acid N, N-dimethyl-(2,4,6-trimethyl puratized agricultural spray), four (2,3,4,6-tetrafluoro phenyl) boric acid Trialkyl ammonium, four (2,3,4,6-tetrafluoro phenyl) boric acid N, N-dialkyl group puratized agricultural spray, four (perfluoronapthyl) Boric ammonium, four (perfluoronapthyl) boric acid N, N-dialkyl group puratized agricultural spray, four (perfluorinated biphenyl) boron Acid trialkyl ammonium, four (perfluorinated biphenyl) boric acid N, N-dialkyl group puratized agricultural spray, the four (double (fluoroforms of 3,5- Base) phenyl) boric ammonium, four (3,5-double (trifluoromethyl) phenyl) boric acid N, N-dialkyl benzene Ammonium, four (double (trifluoromethyl) phenyl of 3,5-) boric acid N, N-dialkyl group-(2,4,6-trimethyl puratized agricultural spray), Four (pentafluorophenyl group) boric acid two (isopropyl) ammonium, (wherein alkyl is methyl, ethyl, propyl group, positive fourth Base, sec-butyl or the tert-butyl group).

Carrier

In some embodiments, complex described herein can be by other coordination of payload Any method of catalyst system is loaded (with and without activator), effectively refers to prepared Catalyst may be used for making olefin oligomerization or polymerization in many phase methods.Catalyst precarsor, activation If conactivator, applicable solvent and carrier that agent needs can add in any order or simultaneously Add.Generally, complex and activator can be combined in a solvent to form solution.Then, add Carrier, and stir described mixture 1 minute-10 hours.Total liquor capacity can be more than carrier Pore volume, but some embodiments limit total liquor capacity to less than forming gel or slurry institute The volume (the about 90%-400% of pore volume, preferably approximately 100-200%) needed.Stirring After mixing, remove residual solvent under vacuo, the most at ambient temperature and more than 10-16 hour. But greater or lesser time and temperature are possible.

Complex can also be supported in the case of there is not activator；It that case, will Activator (if with need conactivator) adds in the liquid phase of polymerization.Additionally, two kinds Or more kinds of different complexes may be located in same vehicle.Similarly, two or more activation Agent or activator and conactivator may be located in same vehicle.

The solid particulate carrier being suitable for generally is made up of, each polymer or refractory oxide material It is preferably porous.Preferably, have more than the particle mean size of 10 μm any carrier material fit Share in the present invention.Various embodiments select porous carrier materials, such as, Talcum, inorganic oxygen Compound, butter (such as magnesium chloride) and resinous support material (such as polystyrene, polyene Hydrocarbon, or polymer complex) or other organic support material any etc..Some embodiments select Inorganic oxide material as carrier material, including the 2nd, 3,4,5,13 or 14 race's metals or Quasi-metal oxide.Some embodiment selecting catalyst carrier materials are to include silicon dioxide, oxygen Change aluminum, silica-alumina and their mixture.Other inorganic oxide can individually or It is used in combination with silicon dioxide, aluminium oxide or silica-alumina.They are magnesium oxide, oxygen Change titanium, zirconium oxide etc..The such as montmorillonite of lewis acidity material can also be served as with similar clay Carrier.In this case, carrier inessential can double as activator component, however, it is also possible to make With additional activator.

Can be by many method pretreated carrier materials.For example, it is possible to calcination inorganic oxide, Carry out chemical treatment with dehydroxylating agent such as aluminum alkylates etc. or this difference all uses.

As it has been described above, polymer support is also by being applicable according to the present invention, see for example Description in WO95/15815 and US5,427,991.Disclosed method can be with the urging of the present invention Agent complex, activator or catalyst system are used together to adsorb on polymer support Or absorb them, if being particularly made up of porous particle, or can be via being bonded to polymer chain Functional group or the bonding of the chemical functional groups in polymer chain.

Useful carrier is generally of 10-700m²The surface area of/g, the hole of 0.1-4.0cc/g Volume and the particle mean size of 10-500 μm.Some embodiments select 50-500m²The surface of/g Long-pending, the pore volume of 0.5-3.5cc/g or the particle mean size of 20-200 μm.Other embodiment Select 100-400m²The surface area of/g, the pore volume of 0.8-3.0cc/g and 30-100 μm Particle mean size.Useful carrier is generally of 10-1000 angstrom, or 50-500 angstrom, or 75-350 Angstrom pore-size.

Catalyst complex described herein is typically pressed 10-100 micromole's complex/gram solid and is carried Body；Or 20-80 micromole's complex/gram solid carrier；Or 40-60 micromole's complex/gram The load level of carrier is deposited on carrier.But greater or lesser value can be used, as long as solid The total amount of complex is preferably more than the pore volume of carrier.

Polymerization

Catalyst complex of the present invention can be used for making the polymerization of conventionally known experience metallocene catalyst The such as polymerization of unsaturated monomers of solution, slurry, gas phase and high pressure polymerisation.Generally, make one or Multiple complex described herein, one or more activators contact with one or more monomers to produce Raw polymer.In some embodiments, complex can be load and so will especially may be used The fixed bed that carries out with single, serial or parallel connection reactor for known, moving bed, fluid bed, Slurry, solution or body operator scheme.

The present invention can use the reactor of one or more serial or parallel connection.Can be by complexation Thing, activator and conactivator when desired flow to reaction individually as solution or slurry Device, just activated before reactor online, or pre-activate giving as activated solution or slurry pump Reactor.It is polymerized and carries out, wherein by monomer, comonomer, catalyst with the operation of single reactor / activator/conactivator, non-essential scavenger and non-essential modifying agent are added to list continuously Individual reactor, or carry out with tandem reactor operation, wherein said components being added to being connected in series Two or more reactors in each in.Catalytic component can be added to described string In the first reactor in connection reactor.Catalytic component can also be added to two reactors In, one of which component is added in the first reactor, and another kind of component adds other reactor to In.In a preferred embodiment, in the presence of alkene, complex is activated in the reactor.

In an especially preferred embodiment, polymerization is continuation method.

Polymerization used herein generally includes and makes one or more olefinic monomers and retouch herein The complex stated (with optionally, activator) contact.For purposes of the invention, alkene is defined as bag Include polyene (such as alkadienes) and only there is the alkene of a double bond.Polymerization can be (the most molten Liquid or polymerisation in bulk) or heterogeneous (slurry in liquid diluent, or the gas in gaseous diluent Phase) polymerization.In the case of heterogeneous slurry or gas-phase polymerization, complex and activator can be loads 's.Silicon dioxide can be used as carrier at this.Chain-transferring agent (such as hydrogen, or diethyl zinc) is permissible Put into practice for the present invention.

Polymerization of the present invention can preferably include about 30 DEG C-about 200 DEG C, preferably 60 DEG C -195 DEG C, carry out under conditions of the temperature of preferably 75 DEG C-190 DEG C.This method can be Carry out under the pressure of 0.05MPa-1500MPa.In a preferred embodiment, pressure is 1.7MPa-30MPa, or in another embodiment, the most at supercritical conditions, pressure Power is 15MPa-1500MPa.

Monomer

Monomer useful herein includes containing 2-20 carbon atom, or the alkene of 2-12 carbon atom (optimal ethylene, propylene, butylene, amylene, hexene, heptene, octene, nonene, decene and ten Two carbenes) and the most also include polyenoid (such as diene).

Complex described herein be particularly useful for making ethylene (individually or with at least one other Ethylenically unsaturated monomer, such as C₃-C₂₀Alpha-olefin, especially C₃-C₁₂Alpha-olefin combines) polymerization. Similarly, complex of the present invention be also particularly useful for making propylene (individually or with at least one other Ethylenically unsaturated monomer such as ethylene or C₄-C₂₀Alpha-olefin, especially C₄-C₂₀Alpha-olefin combines Ground) polymerization.Preferably the example of alpha-olefin include ethylene, propylene, butene-1, amylene-1, oneself Alkene-1, heptene-1, octene-1, nonylene-1, decylene-1, dodecylene-1,4-methylpentene-1, 3-methylpentene-1,3,5,5-trimethylhexene-1 and 5-ethyl nonylene-1.

In an especially preferred embodiment, prepare acrylic polymers, such as Noblen.

In some embodiments, monomer mixture can also be by most 10wt%, such as 0.00001-1.0wt%, such as 0.002-0.5wt%, such as 0.003-0.2wt% comprise one Plant or multiple diene, based on monomer mixture.The limiting examples of useful diene includes ring penta Diene, norbornadiene, dicyclopentadiene, 5-ethidine-2-norborene, 5-vinyl-2- Norborene, 1,4-hexadiene, 1,5-hexadiene, 1,5-heptadiene, 1,6-heptadiene, 6-first Base-1,6-heptadiene, 1,7-octadiene, 7-methyl isophthalic acid, 7-octadiene, 1,9-decadinene and 9-first Base-1,9-decadinene.

Produce short-chain branched alkene when using, such as, during propylene, caltalyst ties up to suitable bar Tacticity polymer can be produced under part or there is in polymer chain the poly-of stereo-sequence Compound.

Scavenger

In some embodiments, when using complex described herein, especially solid when them When being scheduled on carrier, catalyst system also will comprise one or more scavenging compounds.Here, Term scavenging compound refers to remove the compound of polar impurity from reaction environment.These impurity are not Affect catalyst activity and stability sharply.Generally, scavenging compound will be Organometallic compounds Thing such as United States Patent (USP) 5,153,157,5,241,025 and WO-A-91/09882, 13rd race's organometallic of WO-A-94/03506, WO-A-93/14132 and WO 95/07941 Compound.Exemplary compound includes triethyl aluminum, boron triethyl, three-aluminium isobutyl, first Base aikyiaiurnirsoxan beta, isobutyl aluminium alkoxide and three-octyl aluminum.Have and connect with metal or metalloid center Huge or the C connect₆-C₂₀Those scavenging compounds of linear hydrocarbyl substituents generally make to urge with activity The unfavorable interaction of agent minimizes.Example includes triethyl aluminum, but it is further preferred that huge Compound such as three-aluminium isobutyl, three-prenyl aluminum and long-chain linear alkyl-substituted aluminum Compound, such as three-n-hexyl aluminum, three-octyl aluminum or three-dodecyl aluminum.Work as alumina When alkane is used as activator, exceed any excess needed for activation by removal of contamination and additional removing It is unnecessary that property compound is probably.Aikyiaiurnirsoxan beta can also be by clearing amount and other activator, such as MAO, [Me₂HNPh]⁺[B(pfp)₄]^-Or B (pfp)₃(perfluorophenyl=pfp=C₆F₅) together Add.

In a preferred embodiment, by two or more complex and diethyl zinc with One reactor is combined with monomer.Or, by one or more complex and another kind of catalyst (example Such as metallocene) and diethyl zinc be combined with monomer in same reactor.

Polymer product

Although the molecular weight of the polymer prepared at this is by reactor condition, dense including temperature, monomer Degree and pressure, the impact of the existence etc. of chain terminating agent, but the homopolymerization being prepared by the method for the present invention Thing and copolymer products can have the about 1,000-about 2,000,000 measured by GPC G/mol, or about 30,000-about 600,000g/mol, or about 100,000-is about The Mw of 500,000g/mol.Here the preferred polymer prepared can be homopolymer or copolymer. In a preferred embodiment, comonomer presses at most 50mol%, preferably 0.01-40 Mol%, preferably 1-30mol%, preferably 5-20mol% exists.

In some embodiments here, preparing many kurtosis polyolefin composition, it comprises first Polyolefin component and at least another kind of molecular weight are different from the polyolefin of described first polyolefin component Component, it is preferable that GPC trace has more than one peak or flex point.

In a preferred embodiment in accordance with this invention, preparation has 150 DEG C or bigger, preferably 151 DEG C or bigger, preferably 152 DEG C or bigger, preferably 153 DEG C or bigger, preferably 154 DEG C or more Greatly, preferably 155 DEG C or bigger, (Tm, DSC, second time is molten for the fusing point of preferably 156 DEG C or bigger Melt) acrylic polymers (such as HOPP).For the purpose of claim, Tm should This measures as follows.

Differential scanning calorimetry (DSC)

Use differential scanning calorimetry (DSC) at commercial instruments (such as, TA Instruments 2920 DSC) upper measurement Tm melt temperature (also referred to as fusing point).Generally, by 6-10mg molded polymeric It is encapsulated in aluminum dish and at room temperature loads instrument.Melted data (heating for the first time) are by with 10 DEG C Sample is heated to more than its melt temperature (usual for polypropylene 220 DEG C) by the rate of heat addition of/min At least 30 DEG C obtain.Sample is kept at least 5 minutes at such a temperature, to destroy its thermal history. By with the cooldown rate of 20 DEG C/min by sample from melt cooling to crystallization temperature below at least 50 DEG C (usual for polypropylene-50 DEG C) obtain crystal data.Sample is kept at such a temperature to Few 5 minutes, finally with the heating of 10 DEG C/min, to obtain other melted data, (second time added Heat).Turn according to standardization program analysis heat absorption melting transition (the first and second heating) and exothermic crystallization Become.The melt temperature of report is the peak melt temperature from second time heating, unless otherwise prescribed. For showing the polymer at multiple peaks, melt temperature is defined as absorbing heat with maximum from melted trace The peak melt temperature that calorimetric response (relative with the peak occurred at the maximum temperature) is associated.

By such as Macromolecules, coagulating described in 2001, Vol.34, No.19, pg.6812 Glue penetration chromatograph (GPC) measures weight average molecular weight (Mw), number-average molecular weight (Mn) and z average molecular weight (Mz) measurement, described document is fully introduced into herein incorporated by reference, including using equipped with differential refractometer Index-Detector (DRI), equipped with three Polymer Laboratories PLgel 10mm The Temperature Size Exclusion chromatograph (SEC, Waters Alliance 2000) of Mixed-B post.With 1.0 cm³The flow of/min and the volume injected of 300 μ L operate described instrument.It is being maintained at 145 DEG C Baking oven encapsulates various feed-line, post and differential refractometer (DRI detector).Following preparation is poly- Polymer solution: heat under agitation continuously at 160 DEG C and contain～1000ppm butyl filtered Change the 0.75-1.5mg/mL polymer in 1,2,4-(TCB) of hydroxy-methylbenzene (BHT), continue 2 Hour.The sample of the solution containing described polymer is injected in GPC and use filtered containing～ 1,2,4-trichloro-benzenes (TCB) eluting of 1000ppm BHT.With a series of narrow MWD polystyrene marks The separation efficiency of quasi-sample calibration post group, sample intended that the reflection of described separation efficiency is analyzed M_WScope and the exclusion limit of post group.Use from Polymer Laboratories (Amherst, MA) Obtain and peak molecular weight (Mp) is～17 independent polystyrene of 580 to 10,000,000 Standard sample produces calibration curve.Measure every kind of polystyrene standard sample retention volume it Before, each test calibrated fluxes is thought, and flow identifier thing gives shared peak position and (is taken as just injecting Peak).When the sample is analyzed, flowing marker peak position calibrated flow is used.Produce calibration as follows Curve (log (Mp) vs. retention volume): at the peak in the DRI signal of every kind of PS standard sample Record retention volume, and this data set is fitted in second order polynomial.By using with following table Mark shown in B-person of outstanding talent's Brunswick (Mark-Houwink) coefficient determination equivalent molecular weight of polyethylene:

Table B

In a preferred embodiment, the homopolymer being prepared by the method for the present invention and copolymer Product can have about 1, and 000-about 2,000,000g/mol, or about 30,000-is big About 600,000g/mol, or about 100,000-about 500,000g/mol passes through GPC The Mw that measures also has 150 DEG C or bigger, or 151 DEG C or bigger, or 152 DEG C or bigger, Or 153 DEG C or bigger, or 154 DEG C or bigger, or 155 DEG C or bigger, or 156 DEG C Or the bigger Tm measured by DSC.

Terminal use

The goods using the polymer prepared at this to be formed can include, such as, mechanograph is (such as Container and bottle, such as domestic container, container for industrial chemicals, personal care articles bottle, medical treatment Container, fuel tank and storage utensil, toy, sheet material, pipe, pipe arrangement), film, nonwoven Thing etc..Self-evidently, application inventory is merely exemplary above, the most conditional meaning Figure.

In another embodiment, the present invention relates to:

1. in the first aspect of the invention, provide the pyridine radicals two represented by formula (A) or (B) Amido transition metal complex (is optionally used for olefinic polymerization):

Wherein:

M is the 3rd, 4,5,6,7,8,9,10,11 or 12 race's metals；

Q1 is by preferably by formula-G¹-G²-G³Three atomic bridges of-expression are by R²The group connected with Z, The center of wherein said three atoms is preferably to form the 15th or 16 race's elements of coordinate bond with M, Wherein G²It is the atom of the 15th or 16 races, G¹And G³It is respectively the atom of the 14th, 15 or 16 races, Wherein G¹、G²And G³, or G¹And G², or G¹And G³, or G²And G³Monocycle or multi-ring can be formed System, if G¹And/or G³In any one be the atom of the 14th race, then R³⁰And R³¹Bonding On this kind of one or more G atoms, if G¹、G², and/or G³In any one be The atom of 15 races, then R³⁰It is bonded on this kind of one or more G atoms, the most each R³⁰And R³¹ Independently be hydrogen or C₁-C₁₀₀Alkyl；

Q2 is NR¹⁷Or PR¹⁷, wherein R¹⁷Selected from containing 1-20 carbon atom (preferably 2-16, preferably 4-14, preferably 5-12, preferably 6-10 carbon atom) have 1.66 or bigger (or 1.70 or Bigger, or 1.80 or bigger, or 1.83 or bigger) H/C ratio alkyl wherein with N Or the carbon atom of P keyed jointing is not tertiary carbon atom, and wherein R¹⁷Can be unsubstituted or substituted (preferably replacing has 1-5 substituent group, described substituent group to include F, Cl, Br, I, CF₃、NO₂、 Alkoxyl, dialkyl amido, silicyl, siloxy, aryloxy group, aryl and containing 1-10 The alkyl of individual carbon, such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, Nonyl, decyl and their isomer)；

Q3 is-(TT)-or-(TTT)-, the most each T is carbon or hetero atom (preferably C, O, S Or N, described carbon or hetero atom can be unsubstituted (such as, hydrogen with carbon or hetero atom keyed jointing) or Replace and have one or more R³⁰Group), these one or more R³⁰Group and "-C-Q³=C-" fragment one Rise and form 5-or 6-cyclic group or include the polycyclic moiety of described 5 or 6 cyclic group；

R1 is selected from alkyl and substituted alkyl or silicyl；

R²And R¹⁰It is-E (R independently of one another¹²)(R¹³)-, wherein E is carbon, silicon or germanium, each R¹² And R¹³Independently selected from hydrogen, alkyl and substituted alkyl, alkoxyl, silicyl, amino, Aryloxy group, halogen and phosphino-, R¹²And R¹³Can engage to be formed saturated, substituted or unsubstituted Alkyl ring, wherein this ring has 4,5,6 or 7 ring carbon atoms and the wherein substituent group on this ring Can engage to form additional ring, or R¹²And R¹³Can engage to form saturated heterocyclic or full With substituted heterocycle, wherein the substituent group on this ring can engage to form additional ring；

Z is-(R₁₄)pC-C(R₁₅) q-and R₁₄And R₁₅Independently selected from hydrogen, alkyl and substituted hydrocarbon Base, and the most adjacent R₁₄And R₁₅Group can engage to be formed aromatics or saturated, replace or not Substituted alkyl ring, wherein this ring has 5,6,7 or 8 ring carbon atoms and wherein on this ring Substituent group can engage to form additional ring, and p is 1 or 2, and q is 1 or 2；

L is anion leaving group, and wherein this L group can be identical or different and any two L group can connect to form dianion leaving group；

N is 0,1,2,3 or 4；

L' is neutral Lewis base；With

W is 0,1,2,3 or 4；

Wherein n+w is at most 4.

2. the complex of section 1, wherein Q¹Be via 2 and 6 (position on pyridine ring, its Middle nitrogen is 1) in carbon and Z and R²The substituted or unsubstituted pyridine radicals connected.

3. the complex of sections 1 or 2, wherein G¹And G³It is each independently selected from C, N, O and S, Preferably, there is the G of they corresponding R bases¹And G³Be methyl, ethyl, propyl group, butyl, amyl group, Hexyl, octyl group etc., it is preferable that there is the G of they corresponding R bases¹And G³Be formed as ring structure, excellent Select pyridine.

4. the complex of sections 1,2 or 3, wherein Q²It is NR¹⁷。

5. the complex of sections 1,2,3 or 4, wherein Q³It is the three carbon linkers forming pyridine ring Or Q (CH-CH-CH)³It is the two atom linkers containing a carbon and the 15th or 16 race's elements, Described linker is made to form five-ring heterocycles, such as imidazoles or substituted imidazoles.

6. the pyridine radicals diaminourea transition metal complex represented by formula (I) or (II) is (optionally For olefinic polymerization):

Wherein:

M is the 3rd, 4,5,6,7,8,9,10,11 or 12 race's metals；

R17 selected from containing 1-20 carbon atom (preferably 2-16, preferably 4-14, preferably 5-12, excellent Select 6-10 carbon atom) have 1.66 or bigger (or 1.70 or bigger, or 1.80 or more The alkyl of H/C ratio greatly, or 1.83 or bigger), wherein the carbon atom with N keyed jointing is not uncle Carbon atom, and wherein R¹⁷Can be unsubstituted or substituted (preferably replace have 1-5 substituent group, Described substituent group includes F, Cl, Br, I, CF₃、NO₂, alkoxyl, dialkyl amido, first silicon Alkyl, siloxy, aryloxy group, aryl and the alkyl containing 1-10 carbon, such as methyl, Ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl and theirs is different Structure body)；

R1 is selected from alkyl and substituted alkyl or silicyl；

R²And R¹⁰It is-E (R independently of one another¹²)(R¹³)-, wherein E is carbon, silicon or germanium, each R¹² And R¹³Independently selected from hydrogen, alkyl and substituted alkyl, alkoxyl, silicyl, amino, Aryloxy group, halogen and phosphino-, R¹²And R¹³Can engage to be formed saturated, substituted or unsubstituted Alkyl ring, wherein this ring has 4,5,6 or 7 ring carbon atoms and the wherein substituent group on this ring Can engage to form additional ring, or R¹²And R¹³Can engage to form saturated heterocyclic or full With substituted heterocycle, wherein the substituent group on this ring can engage to form additional ring；

L is anion leaving group, and wherein this L group can be identical or different and any two L group can connect to form dianion leaving group；

N is 0,1,2,3 or 4；

L' is neutral Lewis base；With

W is 0,1,2,3 or 4；

Wherein n+w is at most 4；

R³、R⁴And R⁵Independently selected from hydrogen, alkyl, substituted alkyl, alkoxyl, aryloxy group, Halogen, amino and silicyl, and the most adjacent R group (R³&R⁴And/or R⁴&R⁵) can To engage to form substituted or unsubstituted alkyl or the ring of heterocycle, wherein this ring has 5,6,7 Or 8 annular atomses and wherein the substituent group on this ring can engage to form additional ring；With

R⁶、R⁷、R⁸、R⁹、R^15*And R^16*Independently selected from hydrogen, alkyl, substituted alkyl, alcoxyl Base, halogen, amino and silicyl, and the most adjacent R group (R⁶&R⁷, and/or R⁷& R^15*, and/or R^16*&R^15*, and/or R⁸&R⁹) can engage form saturated, replacement or do not take The alkyl in generation or the ring of heterocycle, wherein this ring has 5,6,7 or 8 ring carbon atoms and wherein should Substituent group on ring can engage to form additional ring.

7., according to the complex of either segment in section 1-6, wherein M is Ti, Zr or Hf.

8. according to the complex of either segment, wherein R in section 1-7²It is CH₂。

9. according to the complex of either segment in section 1-8, the most above-mentioned R¹And R³-R⁹And/or R¹¹-R¹⁵ Containing 1-30 carbon atom, particularly 2-20 carbon atom.

10., according to the complex of either segment in section 1-9, wherein E is carbon and R¹And R¹¹Select independently From the phenyl by 0-5 the various replacement of substituent group, this substituent group include F, Cl, Br, I, CF₃、NO₂, alkoxyl, dialkyl amido, alkyl (such as alkyl and aryl) and substituted alkyl (example Such as heteroaryl), wherein group contains 1-10 carbon.

11. according to the complex of either segment in section 1-10, wherein L be or selected from halogen, alkyl, Aryl, alkoxyl, amino, hydrogen-based, phenoxy group, hydroxyl, silicyl, pi-allyl, thiazolinyl And alkynyl；And/or L' is or is selected from ether, thioether, amine, nitrile, imines, pyridine and phosphine.

The complex of either segment, wherein R in 12. sections of 1-11²Represented by with following formula:

Wherein R¹²It is hydrogen, alkyl, aryl or halogen；R¹³It is hydrogen, alkyl, aryl or halogen.

The complex of either segment, wherein R in 13. sections of 1-12⁶, R⁷, R⁸, R⁹, R¹⁵And R *¹⁶The most only On the spot selected from hydrogen, alkyl, substituted alkyl, alkoxyl, halogen, amino and silicyl.

The complex of either segment, wherein R in 14. sections of 1-13¹, R³, R⁴And R⁵Each containing 1-30 Individual carbon atom.

The complex of either segment in 15. sections of 1-14, wherein E is carbon and R¹Have 0 selected from replacement, 1, 2, the phenyl of 3,4 or 5 substituent groups, described substituent group is selected from F, Cl, Br, I, CF₃、NO₂、 Alkoxyl, dialkyl amido, alkyl and substituted alkyl, it contains 1-10 carbon.

The complex of either segment in 16. sections of 1-15, wherein for R¹⁰, E is carbon, R¹²Be phenyl and R¹³It is H.

The complex of either segment, wherein one or more R in 17. sections of 1-16²Group is selected from CH₂、 CMe₂、SiMe₂、SiEt₂、SiPr₂、SiBu₂、SiPh₂, Si (aryl)₂With Si (alkyl)₂、 CH (aryl), CH (Ph), CH (alkyl), CH (2-isopropyl phenyl), and/or one or more R¹⁰Group is selected from CH₂、CMe₂、SiMe₂、SiEt₂、SiPr₂、SiBu₂、SiPh₂, Si (virtue Base)₂With Si (alkyl)₂, CH (aryl), CH (Ph), CH (alkyl), CH (2-isopropyl phenyl), Wherein alkyl is C₁-C₄₀Alkyl, aryl is C₅-C₄₀Aryl, Ph is phenyl.

The complex of either segment, wherein R in 18. sections of 1-17¹⁷It it is cyclohexyl, ring octyl group, ring last of the ten Heavenly stems Base or cyclo-dodecyl.

The complex of either segment, wherein R in 19. sections of 1-18¹⁷Replace have one, two, three, Four or five substituent groups, described substituent group is selected from F, Cl, Br, I, CF₃、NO₂, alkoxyl, Dialkyl amido, aryl and the alkyl containing 1-10 carbon, such as methyl, ethyl, propyl group, fourth Base, amyl group, hexyl, heptyl, octyl group, nonyl, decyl and their isomer.

20. comprise the catalyst system of the complex of either segment in activator and section 1-19.

The catalyst system of 21. section 20, wherein said activator is aikyiaiurnirsoxan beta and/or noncoordinating the moon Ion.

22. section 20 or the catalyst system of 21, wherein said catalyst system is support type.

23. prepare polyolefinic polymerization, including: a) make one or more olefinic monomers and section 20, the catalyst system contact of 21 or 22；And b) obtain olefin polymer, wherein said catalysis Agent have 200kg polymer/mmol transition metal complex/hour or higher activity.

The method of 24. section 23, wherein said monomer comprises ethylene and/or propylene.

The method of 25. section 23, wherein said monomer comprises propylene and the acrylic polymers formed Be there is the melt temperature measured by differential scanning calorimetry of 150 DEG C or bigger.

Embodiment

Complex A and B (present invention) prepared as described below.Complexation is similarly prepared with complex A Thing J, but wherein cyclohexylamine is replaced by cyclooctylamine.Network is prepared as described in US 2012/0071616 Compound C and D (contrasts).Complex K is similarly prepared with complex A, but uses such as US Pyridine radicals two amine ligand of preparation described in 2012/0071616 A1.

4,4,5,5-tetramethyl-2-(2-methyl isophthalic acid-naphthyl)-1,3,2-dioxaborolanes (dioxaborolane) (1): glycol dibromide (～0.3ml) is added at 1000cm³THF In 6.10g (0.25mol) magnesium circle in.Stir this mixture 10min, then in room temperature Under by strong agitation 3.5h add 55.3g (0.25mol) 1-bromo-2-methyl naphthalene.Continue, 46.5g (250mmol) 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxy is added with portion Polymorphs borine.The mixture 15min of stirring gained, is subsequently poured into 1000cm³In cold water. With 3 × 300ml ethyl acetate extraction product.Separate organic layer, washed by water, saline, MgSO₄Upper dry, finally, it is evaporated.The white solid formed is washed by 2 × 75ml pentane, Then it is dried in a vacuum.Yield 47.3g (70%).For C₁₇H₂₁BO₂Analysis meter Calculate: C, 76.14；H,7.89.Find: C, 76.21；H,7.96.¹H NMR(CDCl₃):δ8.12 (m, 1H, 8-H), 7.77 (m, 1H, 5-H), 7.75 (d, J=8.4Hz, 1H, 4-H), 7.44 (m, 1H, 7-H), 7.38 (m, 1H, 6-H), 7.28 (d, J=8.4Hz, 1H, 3-H), 2.63 (s,3H,2-Me),1.48(s,12H,CMe₂CMe₂)。

2-[2-(bromomethyl)-1-naphthyl]-4,4,5,5-tetramethyl-1,3,2-dioxane penta boron Alkane (2): stir 47.3g (176mmol) 4,4,5,5-tetramethyl under an argon atmosphere at 75 DEG C -2-(2-methyl isophthalic acid-naphthyl)-1,3,2-dioxaborolanes, 33.0g (185mmol) NBS, With 0.17g (0.70mmol) benzoyl peroxide at 340ml CCl₄In mixture 14h. The mixture of gained is cooled to room temperature, filter glass sintering feed (a glass frit) (G3), and Filtrate is evaporated.This program produces the beige solid of 62.2g (99%).For C₁₇H₂₀BBrO₂ Analytical calculation: C, 58.83；H, 5.81. find: C, 58.75；H,5.90.¹H NMR(CDCl₃): δ 8.30 (m, 1H, 8-H), 7.84 (d, J=8.3Hz, 1H, 4-H), 7.79 (m,1H,5-H),7.43-7.52(m,3H,3,6,7-H),4.96(s,2H,CH₂Br),1.51 (s,12H,CMe₂CMe₂)。

Cyclohexyl { [1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolanes-2-base)-2-naphthalene Base] methyl amine (3): in argon gas atmosphere by 18.0g (181mmol) cyclohexylamine, 42.1 (129 Mmol) g 2-[2-(bromomethyl)-1-naphthyl]-4,4,5,5-tetramethyl-1,3,2-dioxane Pentaborane, 18.4 grams of (133mmol) K₂CO₃Stir at 80 DEG C with the mixture of 500ml DMF 12h.The mixture of gained is poured in 1200mL water.Extract by 3 × 200ml ethyl acetate Product.The organic extract merged is at Na₂SO₄Then upper being dried be evaporated.Kugelrohr is used to set The standby cyclohexylamine distilling out excess.Produce 29.9g (67%) kermesinus vitreous solid.Right In C₂₃H₃₂BNO₂Analytical calculation: C 75.62；H 8.83；N 3.83.Find: C 75.69； H 8.79；N 3.87.¹H NMR(CDCl₃): δ 8.51 (m, 1H, 8-H are in naphthyl), 7.76 (m 1H, 4-H is in naphthyl), 7.69 (m, 1H, 5-H are in naphthyls), 7.41-7.46 (m, 1H, 7-H are in naphthyl), 7.35-7.39 (m, 1H, 6-H are in naphthyl), 7.18 (m, 1H, 3-H are in naphthyl), 4.16 (s, 2H, CH₂),3.32(m,1H,NH),1.56-1.67 (m,5H,Cy),1.37(s,12H,BPin),1.15-1.25(m,5H,Cy),0.94-1.06 (m,1H,Cy)。

6-{2-[(Cyclohexylamino) methyl]-1-naphthyl } pyridine-2-formaldehyde (4): purge with argon 21.2g(74.1mmol)Na₂CO₃×10H₂O solution in 660ml water and 190ml methanol 30min.In argon gas atmosphere, the solution obtained is added to 29.9 (80.0mmol) cyclohexyl { [1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolanes-2-base)-2-naphthyl] methyl } Amine, 14.0g (80.0mmol) 6-bromopyridine-2-formaldehyde, 4.62g (4.00mmol) Pd (PPh₃)₄ With in the mixture of 780ml toluene.Use mechanical agitator by this mixture reflux 10h, Then room temperature it is cooled to.Separate organic layer, at Na₂SO₄Upper dry, it is evaporated to volume 300ml, Then extract with the 2M HCl of 3 × 300ml.By saturated K₂CO₃Aqueous solution makes the water layer of merging It is basified to pH value 10, then extracts with 3 × 200ml dichloromethane.At Na₂SO₄Upper being dried is closed And organic extract and be evaporated.Produce 23.1g (84%) brown oil.For C₂₃H₂₄N₂O Analytical calculation: C 80.20；H 7.02；N 8.13.Find: C 80.78；H 7.11；N 8.01.¹H NMR(CDCl₃): δ 10.08 (s, 1H, CHO), (m, 2H, 3-H, 4-H are at Py for 7.96-8.03 In), 7.83-7.89 (m, 2H, 8,5-H is in Py), (m, 2H, 5-H are at Py for 7.59-7.64 Neutralize 4-H in naphthyl), 7.39-7.43 (m, 1H, 6-H are in naphthyl), 7.30-7.34 (m, 1H, 7-H are in naphthyl), 7.20-7.23 (m, 1H, 3-H are in naphthyl), 3.56 (m,2H,CH₂), 2.21 (m, 1H, 1-H are in Cy), 1.57-1.66 (m,4H,Cy),1.02-1.11(m,4H,Cy),0.88-0.96(m,2H,Cy)。

N-[(1E)-(and 6-{2-[(Cyclohexylamino) methyl]-1-naphthyl } pyridine-2-base) methylene Base]-2,6-diisopropyl aniline (5): by 9.80g (28.0 in argon gas atmosphere Mmol) 6-{2-[(Cyclohexylamino) methyl]-1-naphthyl } pyridine-2-formaldehyde, 5.55g (31.0 Mmol) 2,6-diisopropyl aniline, the 0.1g TsOH solution backflow in the dry ethanol of 100ml 10h.Then the mixture of gained is cooled to room temperature, is then evaporated.By flash chromatography at silicon On glue 60 (40-63 μm, eluant: hexane-ethylacetate-triethylamine=10:1:1, volume) Purification residue.Produce 10.8g (77%) yellow powder.For C₃₅H₄₁N₃Analytical calculation: C 83.45；H 8.20；N 8.34.Find: C 83.59；H 8.06；N 8.41.¹H NMR(CDCl₃): (m, 1H, 4-H exist for δ 8.39 (m, 1H, 3-H, in Py), 8.35 (s, 1H, CHN), 8.00 In Py), 7.87-7.92 (m, 2H, 4,8-H is in naphthyl), 7.63 (m, 1H, 3-H are at naphthyl In), (m, 3H, 5-H are in Py and 6,7-H for 7.54 (m, 1H, 3-H are in Py), 7.37-7.47 In naphthyl), 7.09-7.17 (m, 3H, 3,4,5-H in naphthyl), 3.69 (m,2H,CH₂N), 3.01 (sept, J=6.8Hz, 2H, CH 2, in 6-diisopropyl phenyl), 2.29 (m, 1H, CH are in Cy), 1.61-1.72 (m, 4H, Cy), 1.52-1.54 (m, 2H, Cy), 1.19 (d, J=6.8Hz, 12H, CH₃2, in 6-diisopropyl phenyl), 1.09-1.11(m,2H,Cy),0.94-0.99(m,2H,Cy)。

N-[(6-{2-[(Cyclohexylamino) methyl]-1-naphthyl } pyridine-2-base) (2-cumene Base) methyl]-2,6-diisopropyl aniline (6): to 3.56 at-80 DEG C in argon gas atmosphere G (18.0mmol) 2-isopropyl bromo benzene is added in pentane in the solution in 80ml THF The 1.7M of 21.0ml (35.7mmol)^tBuLi.Stir the solution 1h of gained at such a temperature. Then, 3.00g (6.00mmol) N-[(1E)-(6-{2-[(Cyclohexylamino) methyl]-1-is added Naphthyl } pyridine-2-base) methylene]-2,6-diisopropyl aniline solution in 20ml THF. The mixture 30min obtained is stirred at-80 DEG C.Continue, add 10ml water, and by this Plant mixture and be heated to room temperature.Dilute the mixture of gained with 100ml water, and use 50ml second Acetoacetic ester extraction crude product.Separate organic layer, at Na₂SO₄Upper dry, and be evaporated.By hurried Chromatograph silica gel 60 (40-63 μm, eluant: hexane-ethylacetate-triethylamine=10:1:1, Volume) upper purification residue.Produce 1.15g (31%) yellow glass matter solid.For C₄₄H₅₃N₃ Analytical calculation: C 84.70；H 8.56；N 6.73.Find: C 84.86；H 8.69；N 6.55.¹H NMR(CDCl₃):δ7.87(m)；7.59-7.74(m)；7.42-7.46(m)；7.14-7.34 (m)；6.99(m)；5.52(d)；5.39(d)；4.80(m)；4.50(m)；3.67(m)； 3.48-3.58(m)；3.18(m)；2.98(m)；2.50-2.55(m)；2.15(m)；2.25 (m)；1.48-1.72(m)；1.03-1.15(m)；0.98-1.01(m)；0.91-0.93(m)； 0.79-0.86(m)。

Complex B. shielding direct light while, by part 6 (0.898g, 1.44mmol), Hf(NMe2)₂Cl₂(dme) (0.616g, 1.44mmol) and toluene (20mL) are in round-bottomed flask Merging and be heated to 95 DEG C, this round-bottomed flask is the release to allow dimethylamine uncapped.At 3h After, make volatile matter evaporation provide yellow solid under nitrogen flowing, use Et₂O washs this Huang up hill and dale Color solid and described two chloro-complexs of 1.11g (1.27mmol) are provided.By this two chloromethylated intermediates It is dissolved in CH₂Cl₂(20mL) in and be added dropwise at Et₂Me in O₂Mg (4.43mL, 1.4 mmol).After 30 minutes, evaporating volatile substances be dried residual the most up hill and dale under nitrogen flowing Excess.Use CH₂Cl₂(10mL) extracted residues filtering.This solution is concentrated to 1mL, Then adding pentane (3mL) causes product to precipitate as yellow microcrystalline solid.Yield 0.99 G, 83%.The spectrum analysis of room temperature H-NMR indicates this product to be the 85:15 rotating diastereomer Mixture.

N-[2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolanes-2-base) benzyl] hexamethylene Amine (7): toluene (250mL) is added to 2-(4,4,5,5-tetramethyl-1,3,2-dioxane penta Borine-2-base) in benzaldehyde (5.0g, 21.54mmol), then add cyclohexylamine (2.37g, 23.89mmol) and formic acid (～1.0mL, 88%) is to form clear solution.Use Dean-Stark Water knockout drum allows this mixture to reflux and collects toluene/water mixture until clarifying.In the completed, This mixture is cooled to room temperature and makes solution evaporation to 100mL.Then by MeOH (200mL) Add to and this reactant mixture adds NaBH the most portionwise₄(1.63g, 43.08mmol).Stir Mix this mixture 20min and with water (5mL) quencher.Solution evaporation is made to 100mL and to add EtOAc(50mL).Use Na₂SO₄It is dried solution and by removal of solvent under reduced pressure, produces white solid. Then Et is added₂O (200mL) dissolves half white solid.Collect residual solids and under reduced pressure do Dry, it is provided that compound 7.Yield: 6.3g, 46.4%.¹H NMR(CD₂Cl₂):δ7.52-7.50 (d,1H),7.28-7.27(m,2H),7.15-7.13(d,1H),4.02(s,2H),3.42 (s,1H),3.15-3.07(m,1H),1.74-1.61(m,5H),1.29 (s,12H),1.19-1.05(m,6H)。

6-(2-((Cyclohexylamino) methyl) phenyl) pyridine-2-formaldehyde (picol inaldehyde) (8): MeOH (90mL) and water (300mL) are added to Na₂CO₃In (2.97g, 28.0mmol) and use N₂Purging 30min.At N₂Under atmosphere, by institute The solution obtained adds compound 7 (7.95g, 25.2mmol), 6-bromopyridine-2-formaldehyde to (4.70g, 25.2mmol) and Pd (PPh₃)₄(1.48g, 1.28mmol) is dissolved in toluene (300 ML) in the mixture in.Make this mixture backflow 12h, be then cooled to room temperature.Separate organic Layer, uses Na₂SO₄It is dried, is evaporated to 100mL and extracts with 2M HCl (3 × 100mL).Will be full And K₂CO₃Aqueous solution add in the water layer of merging until reach pH value 8 and with dichloromethane (3 × 100mL) extraction.At Na₂SO₄It is dried the organic extract merged, and under reduced pressure evaporates.Logical Cross and use dichloromethane EtOAc (80:20, v/v) to isolate product as eluant on silica gel, carry For compound 8.Yield: 1.30g, 17.5%.¹H NMR(CD₂Cl₂):δ10.15 (s,1H),7.98-7.96(m,2H),7.93-7.91(d,1H),7.57-7.52 (m,2H),7.49-7.39(m,2H),3.81(s,2H),2-.49-2.43 (m,1H),1.87-1.84(m,5H),1.30-1.02(m,6H)。

N-((6-(2-((Cyclohexylamino) methyl) phenyl) pyridine-2-base) methylene)-2,6-two Isopropyl aniline (9): add toluene (250mL) to compound 8 (1.44g, 4.89mmol) With in 2,6-DIPA (0.870g, 4.90mmol), then add formic acid (5mL). Use Dean-Stark water knockout drum to allow this mixture to reflux and collect toluene/water mixture until clear Clearly.The mixture of gained is cooled to room temperature, washs with water (100mL), with saline and Na₂SO₄ It is dried and under reduced pressure evaporates.By using hexane-EtOAc (85:15, v/v) conduct on silica gel Eluant isolation product, it is provided that compound 9.Yield: 0.460g, 20.7%.¹H NMR(CD₂Cl₂): δ7.97-7.94(s,1H),7.74(d,1H),7.72(t,1H),7.53 (d,1H),7.50-7.49(t,2H),7.45-7.37(m,2H),7.22-7.16 (d,2H),7.15-7.13(t,1H),3.83(s,2H),3.09-2.99 (sept,2H),2.43-2.36(m,1H),1.79-1.55(m,6H),1.23-1.21 (d,12H),1.18-0.98(m,5H)。

N-((6-(2-((Cyclohexylamino) methyl) phenyl) pyridine-2-base) (2-isopropyl phenyl) Methyl)-2,6-diisopropyl aniline (10): by Et₂O (10mL) add to compound 9 (0.189g, To form clear pale yellow color solution in 0.417mmol).At-80 DEG C, it is added dropwise over 2-cumene The Et of base lithium (0.136g, 1.08mmol)₂O (5mL) solution is to form red-purple solution.Permit Permitted this mixture to get warm again after a cold spell lentamente to ambient temperature overnight.Then add water (50mL) then to add Et₂O(50mL).Separate Organic substance, with saline, then MgSO₄It is dried.The evaporation of volatile matter carries For compound 10, it does not require any purification.Yield: 0.224g, 76.2%.¹H NMR (CD₂Cl₂):δ7.67(t,2H),7.1-7.53(m,10H),7.00(m,3H),5.44 (d,1H),4.40(d,1H),3.69(s,2H),3.11(sept,1H),2.91 (sept,2H),2.24(m,1H),1.5-1.7(m,6H),1.25(d,3H),1.1-1.2 (m,4H),0.97(d,12H),0.93(d,6H)。

Complex A. while shielding direct light, in arrow-necked bottle by ligand 10 (0.224g, 0.390mmol)、Hf(NMe₂)₂Cl₂(dme) (0.167g, 0.390mmol) and toluene (10mL) Merging and be heated to 95 DEG C, this loose closing of arrow-necked bottle aluminium foil is to allow the release of dimethylamine.? After 4h, make volatile matter evaporation provide yellow solid under nitrogen flowing, wash up hill and dale with pentane This yellow solid and described two chloro-complexs of 0.236g (0.287mmol) are provided.By this dichloro Intermediate is dissolved in CH₂Cl₂(6mL) in and be added dropwise at Et₂Me in O₂Mg (1.09mL, 0.344mmol).After 30 minutes, evaporating volatile substances the most under nitrogen flowing Dried residue.Use CH₂Cl₂(5mL) extracted residues filtering.This solution is condensed into oil Residue then adds pentane (3mL) makes product form yellow-orange color crystal.Yield 0.192 G, 63.1%.

Polymerization Example

Table 1 is shown that propylene polymerization data-complex A, B and J and contrast complex C, D And K.From these data, show that the catalyst that the activation by complex A, B and J is formed has The unexpected significantly higher activity than comparative example.It addition, by complex A, B and J The polypropylene that the polypropylene formed is had than being prepared by contrast complex C, D and K is unexpected Higher fusing point.Such as, comparative test 1 and test 3 (tables 1), it can be seen that by complex A The activity that the catalyst formed has exceedes the activity of the catalyst formed by complex C (contrast) 4 times.Thus, it can be concluded that the phenyl of complex C is replaced by cyclohexyl (and produce network Compound A) it is unexpected favourable.It addition, the polypropylene of preparation has than test 3 in test 1 The fusing point of high 15 DEG C of the polypropylene of middle preparation.Comparative test 5 and test 6 (tables 1), we have observed that Similar trend.It can be seen that the activity of the catalyst formed by complex B is to pass through complexation Almost 3 times of the activity of the catalyst that thing D (contrast) is formed.Additionally, formed in test 5 is poly- The polypropylene height of the fusing point of propylene formation middle than test 6 (contrast) is more than 7 DEG C.Therefore, it can break Fixed, the phenyl of complex D is replaced by cyclohexyl (and producing complex B) be unexpected favorably 's.Same trend is applicable to the polymerization (table 1) carried out at 100 DEG C.Comparative test 7 and test 9, Can be seen that the catalyst formed by complex A is than the catalyst tool formed by complex C (contrast) There is more high activity.The polypropylene formed in test 7 also has more poly-than formed in test 9 (contrasts) The higher fusing point of propylene.Thus, it can be concluded that the phenyl of complex C is replaced by cyclohexyl (and Produce complex A) it is unexpected favourable.Comparative test 8 and test 10, it can be seen that by The catalyst that complex B is formed has higher work than the catalyst formed by complex D (contrast) Property.The polypropylene that the polypropylene formed in test 8 also has than being formed in test 10 (contrasts) is higher Fusing point.Thus, it can be concluded that the phenyl of complex D is replaced by cyclohexyl (and produce network Compound B) it is unexpected favourable.

Find that the catalyst formed by the activation of contrast complex K is had than it for propylene polymerization The activity that its complex is much lower.As tested shown in 14-16, catalyst only produces poly-the third of trace Alkene.Therefore, at R¹⁷It is not favourable that place's tert-butyl group replaces.

General polymerization program

Except as otherwise noted, propylene polymerization is carried out in pressure reactor in parallel, its general description At US6,306,658；US6,455,316；US6,489,168；WO 00/09255；And Murphy Et al. J.Am.Chem.Soc., in page 2003,125,4306-4317, each full text draws Enter herein incorporated by reference for US purpose.Although specific amount, temperature, solvent, reactant, instead Answer thing ratio, pressure and other variable generally can change to the next one from an aggregation test, but The following describe the typical polymerization carried out in pressure reactor in parallel.Table 1 below reports specific examination Test.

It is installed to comprise by the glass vial insert weighed in advance and disposable stirring paddle Each reaction vessel of the reactor of 48 single reaction vessels.Then, solvent is added (generally Isohexane) so that total reaction volume (including follow-up interpolation) arrives 4mL.Import propylene gas and by anti- Device container is answered to be heated to their set point of temperature.During this time, add scavenger and/or help to urge Agent and/or chain-transferring agent, such as three-n-octyl in toluene (usual 100-1000nmol) Aluminum.

Content with 800rpm stirring container.Then activator solution (is dissolved in toluene Four (pentafluorophenyl group) boric acid N of 1.1 molar equivalents, N dimethyl aniline) together with 500 microlitre first Benzene injects in reaction vessel together, is then poured into the toluene solution of catalyst (typically, at toluene In 0.40mM, usual 20-40 nanomole catalyst) and another decile toluene (500 microlitre). Equivalent is measured based on molar equivalent relative to the molal quantity of the transition metal in catalyst complex.

Then reaction is made to proceed until having been reached in the past by a certain amount of response time The pressure of scheduled volume.During this time, by reacting with pressurized with compressed air container quencher.Poly- After closing reaction, the glass tubing insert of polymer product and solvent will be comprised from pressure cell and inertia Atmosphere glove box takes out, and uses Genevac HT-12 centrifuge and Genevac VC3000D Vacuum evaporator operates at elevated temperature and reduced pressure and removes volatile component.Then by vial weigh with Measure the productivity of polymer product.The polymer of gained by Rapid GPC (seeing below) analyze with Measure molecular weight and measure fusing point by DSC (seeing below).

In order to measure, by GPC, the value that various molecular weight is correlated with, employing such as US.6,491,816； US6,491,823；US6,475,391；US6,461,515；US6,436,292；US6,406,632； US6,175,409；US 6,454,947；US 6,260,407 and US6,294,388 typically retouches Automatic " Rapid GPC " system stated to carry out Temperature Size Exclusion chromatograph, described each literary composition Offer and be incorporated herein by reference for US purpose.This equipment have a series of three 30cm × 7.5mm line style post, each post comprises PLgel 10 μm, Mix B.Use 580-3,390,000 The polystyrene standard sample of g/mol calibrates this GPC system.With the eluant of 2.0mL/ minute The oven temperature of flow and 165 DEG C operates this system.Use 1,2,4-trichloro-benzenes as eluant. By the concentration of 0.1-0.9mg/mL, polymer samples is dissolved in 1,2,4-trichloro-benzenes.By 250 μ L polymer solution injects in this system.Use INFRARED ABSORPTION or evaporat light scattering ((only testing 19) Detector monitors polymer concentration in eluant.The molecular weight provided is with linear polystyrene mark Do not revise on the basis of quasi-sample.

TA-Q100 instrument carries out differential scanning calorimetry (DSC) measure to measure polymer Fusing point.By sample preannealing 15 minutes at 220 DEG C, then it is allowed to cool to ambient temperature overnight.So After sample is heated to 220 DEG C, then with the speed of 50 DEG C/min with the speed of 100 DEG C/min Cooling.Fusing point is collected during the heating period.

Table 1. propylene homo.Generic condition: four (perfluorophenyl) boric acid N, N-dimethyl puratized agricultural spray (1.1 Equivalent/Hf), three-octyl aluminum (300nmol) isohexane solvent.* comparative example.

All documents described herein, including any priority documents and/or test procedure all with It is incorporated by reference under the reconcilable all permissions of the present invention.Show from above-mentioned general introduction and particular And be clear to be, although have illustrated and described each form of the present invention, but without departing from this Various amendment is may be made that in the case of spirit and scope.And it is therefore not desirable to the present invention is by this Limit.Similarly, term " comprises (comprising) " and thinks and " includes (including) " with term Synonym.Equally, when compositions, element or element group " comprise " above in transitional term, It should be understood that to further contemplate that there is transitional term " substantially by ... composition ", " by ... Composition ", " be selected from " or " it is " the like combinations before the compositions enumerated, element or each element Thing or element group, vice versa.

Claims (25)

1. there is the pyridine radicals diaminourea transition metal complex of formula (A) or (B):

Wherein:

M is the 3rd, 4,5,6,7,8,9,10,11 or 12 race's metals；

Q¹It is by by formula-G¹-G²-G³Three atomic bridges of-expression are by R²The group connected with Z, wherein The center of described three atoms is can be with the 15th or 16 race's elements of M formation coordinate bond, wherein G²It is the atom of the 15th or 16 races, G¹And G³It is respectively the atom of the 14th, 15 or 16 races, wherein G¹、G²And G³, or G¹And G², or G¹And G³, or G²And G³Monocycle or polycyclic system can be formed, If G¹And/or G³In any one be the atom of the 14th race, then R³⁰And R³¹It is bonded to this kind On individual or multiple G atom, if G¹、G²And/or G³In any one be the atom of the 15th race, Then R³⁰It is bonded on this kind of one or more G atoms, the most each R³⁰And R³¹Independently be hydrogen or C₁-C₁₀₀Alkyl；

Q²It is NR¹⁷Or PR¹⁷, wherein R¹⁷Selected from having 1.66 or bigger containing 1-20 carbon atom The alkyl of H/C ratio, wherein the carbon atom with N or P keyed jointing is not tertiary carbon atom, and wherein R¹⁷ Can be unsubstituted or substituted；

Q³Be-(TT)-or-(TTT)-, the most each T is carbon or hetero atom, and described carbon or miscellaneous Atom unsubstituted or substituted can have one or more R³⁰Group, these one or more R³⁰Group and "-C-Q³ " fragment forms 5-or 6-cyclic group or includes that described 5 or 6 cyclic group are many=C-together Cyclic group；

R¹Selected from alkyl and substituted alkyl or silicyl；

R²And R¹⁰It is-E (R independently of one another¹²)(R¹³)-, wherein E is carbon, silicon or germanium, each R¹² And R¹³Independently selected from hydrogen, alkyl and substituted alkyl, alkoxyl, silicyl, amino, virtue Epoxide, halogen and phosphino-, R¹²And R¹³Can engage to form alkyl saturated, substituted or unsubstituted Ring, wherein this ring have 4,5,6 or 7 ring carbon atoms and wherein the substituent group on this ring can connect Close to form additional ring, or R¹²And R¹³Can engage to form saturated heterocyclic or saturated substituted Heterocycle, wherein the substituent group on this ring can engage to form additional ring；

Z is-(R₁₄)_pC-C(R₁₅)_q-and R₁₄And R₁₅Independently selected from hydrogen, alkyl and substituted alkyl, The most adjacent R₁₄And R₁₅Group can engage to form aromatics or saturated, substituted or unsubstituted Alkyl ring, wherein this ring has 5,6,7 or 8 ring carbon atoms and wherein the substituent group on this ring can To engage to form additional ring, p is 1 or 2, and q is 1 or 2；

L is anion leaving group, and wherein this L group can be identical or different and any two L Group can connect to form dianion leaving group；

N is 0,1,2,3 or 4；

L' is neutral Lewis base；With

W is 0,1,2,3 or 4；

Wherein n+w is at most 4.

2. the pyridine radicals diaminourea transition metal complex of claim 1, wherein said complex by Formula (I) or (II) represent:

Wherein:

M is the 3rd, 4,5,6,7,8,9,10,11 or 12 race's metals；

Wherein R¹⁷Selected from containing 1-20 carbon atom have 1.66 or bigger the alkyl of H/C ratio, Wherein the carbon atom with N keyed jointing is not tertiary carbon atom, and wherein R¹⁷Can be unsubstituted or substituted；

R¹Selected from alkyl and substituted alkyl or silicyl；

R²And R¹⁰It is-E (R independently of one another¹²)(R¹³)-, wherein E is carbon, silicon or germanium, each R¹² And R¹³Independently selected from hydrogen, alkyl and substituted alkyl, alkoxyl, silicyl, amino, virtue Epoxide, halogen and phosphino-, R¹²And R¹³Can engage to form alkyl saturated, substituted or unsubstituted Ring, wherein this ring have 4,5,6 or 7 ring carbon atoms and wherein the substituent group on this ring can connect Close to form additional ring, or R¹²And R¹³Can engage to form saturated heterocyclic or saturated substituted Heterocycle, wherein the substituent group on this ring can engage to form additional ring；

L is anion leaving group, and wherein this L group can be identical or different and any two L Group can connect to form dianion leaving group；

N is 0,1,2,3 or 4；

L' is neutral Lewis base；With

W is 0,1,2,3 or 4；

Wherein n+w is at most 4；

R³、R⁴And R⁵Independently selected from hydrogen, alkyl, substituted alkyl, alkoxyl, aryloxy group, halogen Element, amino and silicyl, and the most adjacent R group (R³&R⁴And/or R⁴&R⁵) can connect Closing to form substituted or unsubstituted alkyl or the ring of heterocycle, wherein this ring has 5,6,7 or 8 Substituent group on individual annular atoms and wherein this ring can engage to form additional ring；With

R⁶、R⁷、R⁸、R⁹、R^15*And R^16*Independently selected from hydrogen, alkyl, substituted alkyl, alkoxyl, Halogen, amino and silicyl, and the most adjacent R group (R⁶&R⁷, and/or R⁷&R^15*, And/or R^16*&R^15*, and/or R⁸&R⁹) can engage to form alkyl saturated, substituted or unsubstituted Or the ring of heterocycle, wherein this ring has 5,6,7 or 8 ring carbon atoms and the wherein replacement on this ring Base can engage to form additional ring.

3. the complex of claim 1 or 2, wherein M is Ti, Zr or Hf.

4. the complex of claim 1 or 2, wherein R²Represented by with following formula:

Wherein R¹²It is hydrogen, alkyl, aryl or halogen；And R¹³It is hydrogen, alkyl, aryl or halogen.

5. the complex of claim 2, wherein R⁶, R⁷, R⁸, R⁹, R^15*And R^16*Independently selected from hydrogen, Alkyl, substituted alkyl, alkoxyl, halogen, amino and silicyl.

6. the complex of claim 2, wherein R¹, R³, R⁴&R⁵Each former containing 1-30 carbon Son.

7. the complex of claim 2, wherein E is carbon and R¹0,1,2,3,4 are had selected from replacement Or the phenyl of 5 substituent groups, described substituent group is selected from F, Cl, Br, I, CF₃、NO₂, alkoxyl, Dialkyl amido, alkyl and substituted alkyl, it contains 1-10 carbon.

8. the complex of claim 1 or 2, the most each L is independently selected from halogen, alkyl, virtue Base, alkoxyl, amino, hydrogen-based, phenoxy group, hydroxyl, silicyl, pi-allyl, thiazolinyl and alkynes Base.

9. the complex of claim 1 or 2, the most each L' independently selected from ether, thioether, amine, Nitrile, imines, pyridine and phosphine.

10. the complex of claim 1 or 2, wherein one or more R²Group is selected from CH₂、CMe₂、 SiMe₂、SiEt₂、SiPr₂、SiBu₂、SiPh₂, Si (aryl)₂With Si (alkyl)₂, CH (aryl), CH (Ph), CH (alkyl), CH (2-isopropyl phenyl), wherein alkyl is C₁-C₄₀Alkyl, aryl is C₅-C₄₀Aryl.

The complex of 11. claim 1 or 2, wherein one or more R¹⁰Group is selected from CH₂、CMe₂、 SiMe₂、SiEt₂、SiPr₂、SiBu₂、SiPh₂, Si (aryl)₂With Si (alkyl)₂, CH (aryl), CH (Ph), CH (alkyl), CH (2-isopropyl phenyl), wherein alkyl is C₁-C₄₀Alkyl, aryl is C₅-C₄₀Aryl, Ph is phenyl.

The complex of 12. claim 1 or 2, wherein R¹⁷Be methyl, ethyl, propyl group, normal-butyl, Cyclohexyl, ring octyl group, ring decyl or cyclo-dodecyl.

The complex of 13. claim 1 or 2, its Chinese style A or the Q of B²Middle R¹⁷In group and N Or the carbon atom of P keyed jointing is secondary carbon or wherein R in Formulas I or II¹⁷In group with N keyed jointing Carbon atom is secondary carbon.

The complex of 14. claim 1 or 2, wherein R¹⁷It it is cyclic aliphatic hydrocarbon group.

The 15. pyridine radicals diaminourea transition metal complexes comprising activator and claim 1 or 2 Catalyst system.

The catalyst system of 16. claim 15, wherein said activator is aikyiaiurnirsoxan beta.

The catalyst system of 17. claim 15, wherein said activator is non-coordinating anion.

The catalyst system of 18. claim 15, wherein said activator is non-selected from following material Coordination anion: four (perfluorophenyl) boric acid N, N-dimethyl puratized agricultural spray, four (perfluorophenyl) boric acid first Base two (octadecyl) ammonium, four (perfluorophenyl) boric acid methyl two (C_14-20Alkyl) ammonium, four (perfluor naphthalenes Base) boric acid trimethyl ammonium, four (perfluoronapthyl) boric acid triethyl ammonium, four (perfluoronapthyl) boric acid 3 third Base ammonium, four (perfluoronapthyl) boric acid three (normal-butyl) ammonium, four (perfluoronapthyl) boric acid three (tert-butyl group) Ammonium, four (perfluoronapthyl) boric acid N, N-dimethyl puratized agricultural spray, four (perfluoronapthyl) boric acid N, N-diethyl Puratized agricultural spray, four (perfluoronapthyl) boric acid N, N-dimethyl-(2,4,6-trimethyl puratized agricultural spray), four (perfluor naphthalenes Base) boric acidFour (perfluoronapthyl) borateFour (perfluoronapthyl) boric acid triphenyl PhosphorusFour (perfluoronapthyl) boric acid triethyl-silicaneFour (perfluoronapthyl) boric acid benzene (diazonium), Four (perfluorinated biphenyl) boric acid trimethyl ammonium, four (perfluorinated biphenyl) boric acid triethyl ammonium, four (perfluors Xenyl) boric acid tripropyl ammonium, four (perfluorinated biphenyl) boric acid three (normal-butyl) ammonium, four (perfluorinated biphenyls Base) boric acid three (tert-butyl group) ammonium, four (perfluorinated biphenyl) boric acid N, N-dimethyl puratized agricultural spray, four (perfluors Xenyl) boric acid N, N-diethyl puratized agricultural spray, four (perfluorinated biphenyl) boric acid N, N-dimethyl-(2,4,6- Trimethyl puratized agricultural spray), four (perfluorinated biphenyl) boric acidFour (perfluorinated biphenyl) borateFour (perfluorinated biphenyl) boric acid triphenyl phosphorusFour (perfluorinated biphenyl) boric acid triethyl-silicaneFour (perfluorinated biphenyl) boric acid benzene (diazonium), [the 4-tert-butyl group -PhNMe₂H][(C₆F₃(C₆F₅)₂)₄B], (wherein Ph is phenyl, and Me is methyl).

The catalyst system of 19. claim 15, wherein one or more R¹⁷Group selected from cyclopropyl, Cyclopenta, cyclohexyl, ring octyl group, ring decyl and cyclo-dodecyl.

20. prepare polyolefinic polymerization, including: a) make one or more olefinic monomers and right Require the catalyst system contact of 15 or claim 18；And b) obtain olefin polymer, wherein Described catalyst have 200kg polymer/mmol transition metal/hour or bigger activity.

The method of 21. claim 20, wherein said activator is non-coordinating anion, or aikyiaiurnirsoxan beta.

The method of 22. claim 20, wherein said monomer comprises ethylene.

The method of 23. claim 20, wherein said monomer comprises propylene.

The method of 24. claim 20, wherein said pyridine radicals diaminourea transition metal complex by Load.

The method of 25. claim 20, wherein said monomer comprises propylene and the propylene polymerization formed Thing has the Tm of 150 DEG C or bigger.