CN106432357B

CN106432357B - Benzene generation -2,9- bis-imine pyridine and cycloheptane iron and cobalt complex catalyst and the preparation method and application thereof

Info

Publication number: CN106432357B
Application number: CN201510487737.5A
Authority: CN
Inventors: 黄放; 张文娟; 孙文华; 胡信全
Original assignee: Institute of Chemistry CAS
Current assignee: Institute of Chemistry CAS
Priority date: 2015-08-10
Filing date: 2015-08-10
Publication date: 2019-03-08
Anticipated expiration: 2035-08-10
Also published as: CN106432357A

Abstract

The present invention relates to benzene generation -2,9- bis-imine pyridine and cycloheptane iron and cobalt complex catalyst and the preparation method and application thereof.The metal complexes are reacted for catalyzed ethylene polymerization, are shown very high catalytic activity, are respectively reached 1.56 × 10⁷g·mol^‑1(Fe)·h^‑1And 1.42 × 10⁷g·mol^‑1(Co)·h^‑1, and such composition catalyst can still keep higher lasting activity at relatively high temperatures, have extensive prospects for commercial application.

Description

Benzene generation -2,9- bis-imine pyridine and cycloheptane iron and cobalt complex catalyst and its system Preparation Method and application

Technical field

The invention belongs to cooperate catalytic field, and in particular to a kind of benzene generation -2,9- bis-imine pyridine and cycloheptane iron and cobalt Complex, preparation method and its application in catalyzed ethylene polymerization.

Background technique

Polyolefin has obtained extensively as important one of synthetic material in daily life and industrial and agricultural production Application, good opportunity to develop and potential development prospect all show this kind of material will be still with faster speed from now on Degree development.Polyolefin industry is that Ziegler-Natta type catalyst development and application in the 1950s flourish later Come, has 60 years developing histories so far.From initial Ziegler-Natta catalyst, oneself develops to current efficient height Performance catalyst, the eighties in last century and the nineties develop metallocene catalyst and late transition metal catalyst, shape again in succession At the pattern of current multiple catalysts joint development, polyolefin is also changed from versatile material to functionalization material.Currently, industrial The polyethylene catalysts of change have Ziegler-Natta type catalyst (DE Pat 889229 (1953)；IT Pat536899 (1955) and IT Pat 545332 (1956)；Chem.Rev., 2000,100,1169), Phillips type catalyst (Belg.Pat.530617(1955)；Chem.Rev.1996,96,3327) and metallocene type catalyst (H.Sinn and W.Kaminsky, Angew.Chem.Int.Ed.Engl., 1980,19,390), and the late transition metal developed in recent years The efficient ethylene oligomerization and polymerization catalyst of complex type.

Nineteen ninety-five, Brookhart study group reports alpha-diimine nickel (palladium) complex, and can be efficiently catalyzed ethylene poly- It closes, and obtains the polymer of high molecular weight and the various degrees of branching.The discovery changes people it has long been believed that late transition metal It is only used for causing olefin(e) oligomerization and being difficult to high poly- idea, late transition metal catalyst catalysis in olefine polymerization has been led to study Upsurge (J.Am.Chem.Soc., 1995,117,6414)；Then, in 1998, Brookhart and Gibson study group is distinguished Pyridine diimine iron, cobalt complex are independently reported, under MAO activation, high ethylene catalyst activity is shown, from this initiation (its structure is shown below ((a) for new step on one new neck in late transition metal catalyzed ethylene polymerization field J.Am.Chem.Soc.,1998,120,4049；(b)Chem.Commun.,1998,849):

Around the basic skeleton structure of pyridine diimine, our seminars are transformed the ligand of such catalyst, Successful design and the catalyst (following formula Fe1-Fe3) for developing multiclass ethylene oligomerization and polymerization.Wherein coordination bone having the same Three kinds of iron series complex Fe1-Fe3 of frame are demonstrated by completely different catalysis characteristics in the presence of co-catalyst MAO: Fe1 is not urged Change activity, Fe2 ethylene oligomerization with higher activity, and Fe3 be demonstrated by higher ethylene polymerization activity (Polym.Int., 2002,51,994；Chin.J.Polym.Sci.,2002,20,205).These results of study are also our purposive designs And the model for synthesizing high activated catalyst is laid a good foundation.

Inventor has then designed and developed the catalyst system (M1, M2, M3 and M4) of several new tridentate coordinations, achieves It is good as a result, they show excellent performance.Wherein, 2- benzimidazole -6- amido pyridine iron and cobalt complex M1 energy Enough highly active catalytic ethylene oligomerizations and polymerization (Chinese Patent Application No. 200610165446.5, December 20 2006 applying date Day).And 2- benzoxazoles -6- amido pyridine iron and cobalt complex M2 can obtain oligomer with more highly active catalytic ethylene oligomerization With polyethylene wax (Chinese Patent Application No. 200810239477.x, December 11 2008 applying date).Especially class in 2005 2- amido -1,10- phenanthroline the iron of topic group exploitation and the complex M3 of cobalt, with the active (Chinese patent of high ethylene oligomerization Application number 200510066427.2, April 22 2005 applying date；Authorized announcement date on March 5th, 2008；Authorization Notice No. CN100372609C).Such catalyst activity can compare favourably with classical pyridine diimine iron catalyst.Meanwhile inventor sets The 2,8- diimine quinoline M4 (Organometallics, 2010,29,1168) of the three tooth nitrogen coordination of meter synthesis is for being catalyzed second Alkene polymerization reaction also shows high catalytic activity, and resulting polymers molecular weight is high, narrow molecular weight distribution, catalyst pair Industrial operation temperature has identical property well, has application potential.

And in nearest a few thing, design introduces condensed ring and cycloaliphatic ring in pyridine diimine structure, it is intended to set Count the superior catalyst of synthesis performance.After being initially charged into most commonly seen six-membered ring structure, 2,8- diimines -5,6,7- Three hydrogen quinoline iron, cobalt complex M5 show ethylene polymerization activity more higher than simple pyridine diimine iron, cobalt, while High ethylene polymerization activity is still kept under higher reaction temperatures, and there is potential commercial application potentiality.Wherein iron complex is catalyzed Vinyl polymerization obtains High molecular weight polyethylene (Organometallics, 2012,31,5039-5048), and cobalt complex is catalyzed Vinyl polymerization obtains the polymerizate (Appl.Catal.A.Gen.2012,447-448) of Narrow Molecular Weight Distribution.It is sub- in pyridine two After introducing heptatomic ring in amine skeleton structure, catalyst thermal stability and higher ethylene polymerization activity (Dalton have been obtained Trans.,2014,43,16818-16829).In order to preferably improve the thermal stability and ethylene polymerization activity of catalyst, also for Deeper into the influence to catalytic performance of research substituent group, we introduce benzene in the skeleton of pyridine diimine and cycloheptane Base, and iron series, cobalt complex have been synthesized for vinyl polymerization research, obtain the good catalyst system of excellent thermal stability And very high ethylene polymerization activity.

Late transition metal complex catalyst structure is easy to modify, and regulates and controls product (polymer and oligomer) structure with this And molecular weight.However, still there are also the difficulties of some basic research during Industrialization as catalyst system of new generation Point and restraining factors.In general, late transition metal catalyst easily inactivates at high temperature, due to chain tra nsfer terminate rate be with The raising of temperature and increase and the thermal stability of complex itself is poor, increase so as to cause activity with reaction temperature and It reduces.This limits the industrially application study of metal complex catalysts to a certain extent.How more high activity is obtained Ethylene rolymerization catalyst and can be kept in high temperature high ethylene polymerization activity become research core content, be also that can use up Industrialized key is promoted fastly.Iron series, the Co catalysts of designed synthesis of the invention, are still able to maintain very high at high temperature Ethylene polymerization activity has great commercial application potentiality.And illustrates that such composition catalyst has and promote research Value.

Summary of the invention

The present invention provides a kind of generation -2,9- bis-imine pyridine of benzene shown in Formulas I and cycloheptane iron and cobalt complex:

Wherein, Ar¹、Ar²、Ar³It is independently from each other

Each R¹、R²、R³、R⁴、R⁵Under being independently from each other H, F, Cl, Br, I or optionally being replaced by one or more R ' Column group: C_1-6Alkyl-, C_1-6Alkyl oxy-, C_3-10Naphthenic base-, C_3-10Cycloalkyl oxy-, C_6-14Aryl-, C_6-14Aryl oxide Base-；

The following groups that each R ' is replaced independently selected from F, Cl, Br, I or optionally by one or more R ": C_1-6Alkyl-, C_1-6Alkyl oxy-, C_3-10Naphthenic base-, C_3-10Cycloalkyl oxy-, C_6-14Aryl-, C_6-14Aryloxy-；

Each R " is independently selected from F, Cl, Br, I, C_1-6Alkyl-, C_1-6Alkyl oxy-, C_6-14Aryl-, C_6-14Aryl oxide Base-；

M is selected from Fe or Co；

X¹、X²It is independently from each other Cl or Br.

In exemplary embodiment of the subject disclosure, above-mentioned group, which has, such as gives a definition:

R¹、R²、R³、R⁴、R⁵The following base for being independently from each other H, F, Cl, Br, I or optionally being replaced by one or more R ' Group: C_1-6Alkyl-, C_1-6Alkyl oxy-, C_6-14Aryl-, C_6-14Aryloxy-；

The following groups that each R ' is replaced independently selected from F, Cl, Br, I or optionally by one or more R ": methyl, second Base, propyl, isopropyl, methoxyl group, ethyoxyl, phenyl, phenoxy group；

Each R " is independently selected from F, Cl, Br, I, methyl, ethyl, propyl, isopropyl, methoxyl group, ethyoxyl, phenyl, benzene Oxygroup.

As example, R¹、R²、R³、R⁴、R⁵It is independently from each other H, F, Cl, Br, I or is optionally taken by one or more R " Methyl, ethyl, propyl, isopropyl, methoxyl group, ethyoxyl, the C in generation_6-14Aryl C_1-6Alkyl-, two C_6-14Aryl C_1-6Alkyl-, example Such as phenyl methyl, phenylethyl, diphenyl methyl, diphenyl-ethyl, naphthyl methyl, naphtylethyl group, dinaphthyl ylmethyl, dinaphthyl Ethyl；

Term " C_1-6Alkyl " is interpreted as the preferred linear or branching for indicating to have 1,2,3,4,5 or 6 carbon atom It is saturated monovalent hydrocarbon, such as methyl, ethyl, propyl, butyl, amyl, hexyl, isopropyl, isobutyl group, sec-butyl, tert-butyl, different Amyl, 2- methyl butyl, 1- methyl butyl, 1- ethyl propyl, 1,2- dimethyl propyl, neopentyl, 1,1- dimethyl propyl, 4- Methyl amyl, 3- methyl amyl, 2- methyl amyl, 1- methyl amyl, 2- ethyl-butyl, 1- ethyl-butyl, 3,3- dimethyl butyrate Base, 2,2- dimethylbutyl, 1,1- dimethylbutyl, 2,3- dimethylbutyl, 1,3- dimethylbutyl or 1,2- dimethyl butyrate Base or their isomers.Particularly, the group has 1,2,3 or 4 carbon atom (" C_1-4Alkyl "), such as methyl, second Base, propyl, butyl, isopropyl, isobutyl group, sec-butyl, tert-butyl, more particularly, the group have 1,2 or 3 carbon atom (“C_1-3Alkyl "), such as methyl, ethyl, n-propyl or isopropyl.

Term " C_3-10Naphthenic base " be understood to mean that saturation monovalent monocyclic or bicyclic hydrocarbon ring, have 3,4,5,6,7, 8,9 or 10 carbon atoms.The C_3-10Naphthenic base can be monocycle alkyl, such as cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, ring Heptyl, cyclooctyl, cyclononyl or cyclodecyl or for example decahydronaphthalene naphthalene nucleus of bicyclic alkyl.

Term " C_6-14Aryl " is interpreted as preferred one indicated with 6,7,8,9,10,11,12,13 or 14 carbon atoms Monocyclic, bicyclic or tricyclic the hydrocarbon ring (" C of valence armaticity or partial aromatic_6-14Aryl "), especially with the ring of 6 carbon atoms (“C₆Aryl "), such as phenyl；Or xenyl, or the ring (" C with 9 carbon atoms₉Aryl "), such as indanyl or indenes Base, or the ring (" C with 10 carbon atoms₁₀Aryl "), such as tetrahydro naphthyl, ihydro naphthyl or naphthalene, or tool There is the ring (" C of 13 carbon atoms₁₃Aryl "), such as fluorenyl, or the ring (" C with 14 carbon atoms₁₄Aryl "), such as Anthryl.

As example, metal complex of the present invention is selected from any one following complex:

Fe-1:Ar³=Ph；Ar¹And Ar²In: R¹=Me, R²=H, R³=H, R⁴=H, R⁵=Me, M=Fe, X¹=X²= Cl；

Fe-2:Ar³=Ph；Ar¹And Ar²In: R¹=Et, R²=H, R³=H, R⁴=H, R⁵=Et, M=Fe, X¹=X²= Cl；

Fe-3:Ar³=Ph；Ar¹And Ar²In: R¹=i-Pr, R²=H, R³=H, R⁴=H, R⁵=i-Pr, M=Fe, X¹=X² =Cl；

Fe-4:Ar³=Ph；Ar¹And Ar²In: R¹=Me, R²=H, R³=Me, R⁴=H, R⁵=Me, M=Fe, X¹=X²= Cl；

Fe-5:Ar³=Ph；Ar¹And Ar²In: R¹=Et, R²=H, R³=Me, R⁴=H, R⁵=Et, M=Fe, X¹=X²= Cl；

Fe-6:Ar³=Ph；Ar¹And Ar²In: R¹=F, R²=H, R³=H, R⁴=H, R⁵=F, M=Fe, X¹=X²=Cl；

Fe-7:Ar³=Ph；Ar¹And Ar²In: R¹=Cl, R²=H, R³=H, R⁴=H, R⁵=Cl, M=Fe, X¹=X²= Cl；

Fe-8:Ar³=Ph；Ar¹And Ar²In: R¹=Br, R²=H, R³=H, R⁴=H, R⁵=Br, M=Fe, X¹=X²= Cl；

Fe-9:Ar³=Ph；Ar¹And Ar²In: R¹=Ph₂CH,R²=H, R³=Me, R⁴=H, R⁵=Ph₂CH, M=Fe, X¹= X²=Cl；

Co-1:Ar³=Ph；Ar¹And Ar²In: R¹=Me, R²=H, R³=H, R⁴=H, R⁵=Me, M=Co, X¹=X²= Cl；

Co-2:Ar³=Ph；Ar¹And Ar²In: R¹=Et, R²=H, R³=H, R⁴=H, R⁵=Et, M=Co, X¹=X²= Cl；

Co-3:Ar³=Ph；Ar¹And Ar²In: R¹=i-Pr, R²=H, R³=H, R⁴=H, R⁵=i-Pr, M=Co, X¹=X² =Cl；

Co-4:Ar³=Ph；Ar¹And Ar²In: R¹=Me, R²=H, R³=Me, R⁴=H, R⁵=Me, M=Co, X¹=X²= Cl；

Co-5:Ar³=Ph；Ar¹And Ar²In: R¹=Et, R²=H, R³=Me, R⁴=H, R⁵=Et, M=Co, X¹=X²= Cl；

Co-6:Ar³=Ph；Ar¹And Ar²In: R¹=F, R²=H, R³=H, R⁴=H, R⁵=F, M=Co, X¹=X²=Cl；

Co-7:Ar³=Ph；Ar¹And Ar²In: R¹=Cl, R²=H, R³=H, R⁴=H, R⁵=Cl, M=Co, X¹=X²= Cl；

Co-8:Ar³=Ph；Ar¹And Ar²In: R¹=Br, R²=H, R³=H, R⁴=H, R⁵=Br, M=Co, X¹=X²= Cl；

Co-9:Ar³=Ph；Ar¹And Ar²In: R¹=Ph₂CH,R²=H, R³=Me, R⁴=H, R⁵=Ph₂CH, M=Co, X¹= X²=Cl.

Wherein, Me represents methyl, and Et represents ethyl, and i-Pr represents isopropyl, and F represents fluorine, and Cl represents chlorine, and Br represents bromine, Ph represents phenyl, Ph₂CH represents benzhydryl.

The present invention also provides the preparation methods of Formulas I complex, including by Formula IV and VII compound and FeCl₂·4H₂O or CoCl₂Reaction, obtains Formulas I complex:

Wherein, R¹、R²、R³、R⁴、R⁵And Ar³With the group definition in above-mentioned Formulas I.

The actual conditions and parameter of above-mentioned reaction are not particularly limited, those skilled in the art can be according to specific feelings Condition selects specific reaction condition and parameter, to prepare target compound.Describe to following exemplary the available item of the reaction Wherein one or more conditions and parameter can be applied to the reaction by part and parameter, those skilled in the art, alternatively, can also be with Further modification or adjustment are carried out to them.

Compound and FeCl shown in Formula VII₂·4H₂O or CoCl₂Molar ratio be 1.00~1.05:0.90~ 1.00, such as 1.00:0.90；

Preferably, the reaction is carried out in the presence of acetic acid, more preferably uses acetic acid as solvent；Preferably, described anti- It should be back flow reaction, reaction temperature can be 140 DEG C；Preferably, the reaction time is 4-8 hours, such as 6 hours.

Preferably, the reaction carries out under inert gas (such as nitrogen, argon gas or its gaseous mixture) protection.

According to the present invention, the above method can also include the following steps: compound shown in Formula IV, VII and FeCl₂· 4H₂O or CoCl₂The solution concentration of complex shown in obtained Formulas I is reacted, and poor solvent (such as ether) precipitating, filtering is added Sediment is collected, and the sediment is washed with poor solvent (such as ether) to get target Formulas I complex.

The present invention also provides compounds shown in a kind of Formula VII:

Wherein, Ar³With definition described above.

The present invention also provides the preparation methods of Formula VII compound, include the following steps:

1) Formula II compound is reacted with cyanylation agent (such as potassium ferrocyanide), obtains formula III compound；

2) formula III compound is reacted with ethylene glycol progress ketone protection, obtains formula IV compound；

3) formula IV compound and grignard reagent A r³MgX reaction, obtains Formula V compound；

4) Formula V compound carries out deprotection reaction, obtains Formula VII compound；

Wherein Ar³With definition described above, X is selected from Cl or Br.

In step 1):

The molar ratio of compound shown in cyanylation agent and Formula II can be 0.20-0.30:1, such as 0.25:1；Instead It should preferably be carried out in the presence of Raney nickel (such as 1, bis- (diphenylphosphine) the propane nickel chlorides of 3-), the additional amount of Raney nickel It can be 2%~5% of compound mole shown in Formula II；Cyanalation reaction can carry out in organic solvent；It is described organic Solvent can be selected from least one of n,N-Dimethylformamide and N-Methyl pyrrolidone, preferably N- crassitude Ketone；Cyanalation reaction can carry out under reflux conditions, and the reaction time of the reaction can be 8-16 hours, and specially 12 is small When.

In step 2):

The molar ratio of compound and ethylene glycol shown in formula III can be 1:1.5~2.5, such as 1:2.0；React excellent It is selected in p-methyl benzenesulfonic acid to carry out as under conditions of catalyst, the additional amount of p-methyl benzenesulfonic acid can be compound shown in formula III The 10%-20% of quality；Reaction can carry out in organic solvent；The organic solvent is selected from toluene, dimethylbenzene and 1,4- bis- At least one of six ring of oxygen, preferably toluene；Reaction can carry out under reflux conditions, and the reaction time of the reaction is 8- 16 hours, such as 12 hours.

In step 3):

The molar ratio of compound and Grignard Reagent shown in formula IV can be 1:1.5-2.5, such as 1:2.0；React excellent It is selected under the protection of inert gas (such as nitrogen, argon gas or its mixed gas) and carries out；Reaction can carry out in organic solvent； The organic solvent can be selected from least one of tetrahydrofuran and anhydrous ether, preferably tetrahydrofuran；Reaction can be It being carried out under cryogenic conditions, reaction temperature can be between -10 DEG C -0 DEG C, such as -5 DEG C；The reaction time of reaction can be small for 0.5 When.

In step 4):

Reaction preferably carries out under conditions of p-methyl benzenesulfonic acid is as catalyst, and the additional amount of p-methyl benzenesulfonic acid can be formula The 10%-20% of V compound quality, such as 15%；Reaction can carry out in organic solvent, and the organic solvent can be selected from Acetone, Isosorbide-5-Nitrae-one of dioxane and water or a variety of mixed solvents, for example, Isosorbide-5-Nitrae-dioxane and water mixed solvent, The mixed solvent of acetone and water, the preferably mixed solvent of Isosorbide-5-Nitrae-dioxane and water.The body of in the mixed solvent, organic solvent and water Product is than that can be 1~2:1~2, such as 1:1；Reaction can carry out under reflux conditions, and the reaction time can be 4-8 hours, example Such as 6 hours.

Can also include following one or more purification steps in the preparation method of above-mentioned Formula VII compound:

A) purification step of formula III compound:

The resulting formula III compound of step 1) is dissolved in organic solvent (such as methylene chloride), silicagel column carries out column layer Analysis, using ethyl acetate: petroleum ether=1:4 or methylene chloride: petroleum ether=1:2 is eluted as eluant, eluent, passes through thin layer color Spectrum detection eluted fraction, removes solvent, the formula III compound purified；

B) purification step of formula IV compound:

The resulting formula IV compound of step 2) is dissolved in organic solvent (such as methylene chloride), silicagel column carries out column layer Analysis, using ethyl acetate: petroleum ether=1:10 or methylene chloride: petroleum ether=1:5 is eluted as eluant, eluent, passes through thin layer color Spectrum detection eluted fraction, removes solvent, the formula IV compound purified.

C) purification step of Formula VII compound:

The resulting Formula VII compound of step 4) is dissolved in organic solvent (such as methylene chloride), silicagel column carries out column layer Analysis, using ethyl acetate: petroleum ether=1:10 or methylene chloride: petroleum ether=1:5 is eluted as eluant, eluent, passes through thin layer color Spectrum detection eluted fraction, removes solvent, the Formula VII compound purified.

The present invention also provides a kind of carbon monoxide-olefin polymerics for being used for olefinic polymerization, especially vinyl polymerization, including Formulas I Complex and optional co-catalyst；

The co-catalyst may include one in methylaluminoxane (MAO) and modified methylaluminoxane (MMAO) Kind or two kinds.

The molar ratio of ferro element can be 1000~3500:1 in the co-catalyst and Formulas I complex, preferably 2000 ~2500:1.

The molar ratio of cobalt element can be 1000~3000:1 in the co-catalyst and Formulas I complex, preferably 1500 ~2500:1.

The present invention also provides a kind of methods for preparing polyolefin, especially polyethylene, including in catalyst of the invention In the presence of composition, alkene (such as ethylene) is made to carry out catalytic polymerization.

The exemplary condition of the polymerization reaction includes:

Co-catalyst in iron complex carbon monoxide-olefin polymeric is MAO and the polymerization reaction carries out under normal pressure, described The polymerization temperature of polymerization reaction is 0-30 DEG C, and preferably 10 DEG C, the normal pressure is 1atm.

Co-catalyst in iron complex carbon monoxide-olefin polymeric is MAO and the polymerization reaction carries out under elevated pressure, described The polymerization temperature of polymerization reaction is 40-80 DEG C, preferably 60 DEG C, described to be pressurised into 1atm-10atm, but does not include 1atm.

Co-catalyst in iron complex carbon monoxide-olefin polymeric is MMAO and the polymerization reaction carries out under normal pressure, described The polymerization temperature of polymerization reaction is 0-40 DEG C, and preferably 10 DEG C, the normal pressure is 1atm.

Co-catalyst in iron complex carbon monoxide-olefin polymeric is MMAO and the polymerization reaction carries out under elevated pressure, described The polymerization temperature of polymerization reaction is 50-90 DEG C, preferably 70 DEG C, described to be pressurised into 1atm-10atm, but does not include 1atm.

Co-catalyst in cobalt complex catalyst composition is MAO and the polymerization reaction carries out under normal pressure, described The polymerization temperature of polymerization reaction is 0-60 DEG C, preferably 40 DEG C；The normal pressure is 1atm；

Co-catalyst in cobalt complex catalyst composition is MAO and the polymerization reaction carries out under elevated pressure, described The polymerization temperature of polymerization reaction is 40-80 DEG C, preferably 60 DEG C；It is described to be pressurised into 1atm-10atm, but do not include 1atm；

Co-catalyst in cobalt complex catalyst composition is MMAO and the polymerization reaction carries out under normal pressure, described The polymerization temperature of polymerization reaction is 10-60 DEG C, preferably 30 DEG C；The normal pressure is 1atm；

Co-catalyst in cobalt complex catalyst composition is MMAO and the polymerization reaction carries out under elevated pressure, described The polymerization temperature of polymerization reaction is 50-90 DEG C, preferably 70 DEG C；It is described to be pressurised into 1atm-10atm, but do not include 1atm；

The polymerization time of polymerization reaction can be 10min-60min, such as 30min.

Polymerization reaction can carry out in a solvent；The solvent is selected from one or both of toluene and n-hexane, preferably Toluene.

Polymerization reaction can carry out in inert atmosphere (such as nitrogen).

The present invention also provides Formulas I complexs in preparing olefin polymerization catalysis, especially ethylene rolymerization catalyst Using.

The present invention designed and synthesized contain N ' N ' N '-dentate benzene generation -2,9- bis-imine pyridine and cycloheptane iron and Cobalt complex, the metal complexes react for catalyzed ethylene polymerization, show very high catalytic activity, respectively reach 1.56 ×10⁷g·mol^-1(Fe)·h^-1And 1.42 × 10⁷g·mol^-1(Co)·h^-1, and such composition catalyst is higher At a temperature of can still keep higher lasting activity, have extensive prospects for commercial application.

Detailed description of the invention

Fig. 1 is cobalt complex Co-3 (Ar shown in Formulas I³=Ph；Ar¹And Ar²In: R¹=i-Pr, R²=H, R³=H, R⁴=H, R⁵=i-Pr, M=Co, X¹=X²=Cl) crystal structure schematic diagram.

Specific embodiment

The present invention will be described below by way of specific embodiments, but the present invention is not limited thereto.

Experimental method described in following embodiments is unless otherwise specified conventional method；The reagent and material, such as Without specified otherwise, commercially obtain.

Embodiment 1, preparation (E)-N- (((E) -9- (2,6- diisopropyl aniline) -6,7,8,9- tetrahydro cycloheptane and pyrrole Pyridine -2- benzyl enamine closes frerrous chloride [Fe-3:Ar³=Ph；Ar¹And Ar²In: R¹=i-Pr, R²=H, R³=H, R⁴=H, R⁵= I-Pr, M=Fe, X¹=X²=Cl]

1) chloro- 5,6,7,8- tetrahydro cycloheptane pyridine of 2--under nitrogen protection, is sequentially added into 150ml four-hole boiling flask 9- ketone (7.6g, 40mmol), potassium ferrocyanide (4.4g, 10mmol), 1,3- bis- (diphenylphosphine) propane nickel chlorides (0.65g, It 3mol%) is warming up to 150 DEG C of back flow reactions with N-Methyl pyrrolidone 100ml, oil bath and stays overnight, raw material converts completely.Stop adding Heat, silica gel post separation.Petroleum ether: ethyl acetate=4:1 goes out target product, is yellow solid powder 4.2g, as formula III Shown compound, yield 56.5%.

2) it is sequentially added into 500ml single-necked flask formula III compound (8.0g, 43mmol), ethylene glycol (5.3g, 86mmol), p-methyl benzenesulfonic acid (0.8g, 10%w/w) and 300ml toluene, oil bath are warming up to refluxing toluene 12h, vapor detection, Raw material converts completely.Toluene, silica gel column chromatography is removed under reduced pressure.Petroleum ether: ethyl acetate=10:1 goes out target product, is yellowish Color needle powder 8.0g, as compound shown in formula IV, yield 81.9%.

3) under nitrogen protection, into 250ml Jacketed bottle be added formula IV shown in compound (5.7g, 25mmol) and 100ml tetrahydrofuran leads to -5 DEG C of ethanol baths, phenyl-magnesium-bromide Grignard Reagent (1M, 50ml) is added into system, after being added dropwise to complete Stir half an hour.10ml water quenching reaction is added dropwise, stops stirring, stratification after half an hour.Separate water after upper organic layer Layer is extracted with 3 methylene chloride of 50ml x, is merged organic layer and is concentrated to dryness.Obtain yellow oil 7.4g, as Formula V shownization Close object, yield 95.8%.

4) grease is shifted into 250ml single port bottle, and water and each 75ml of Isosorbide-5-Nitrae-dioxane, p-methyl benzenesulfonic acid is added 1.1g, 90 DEG C of oil baths reflux 6h, vapor detection discovery raw material have converted completely.Stop heating, be cooled to room temperature, is concentrated under reduced pressure, Water phase is extracted with dichloromethane three times.Silica gel column chromatography after concentration.Petroleum ether: ethyl acetate=10:1 goes out target product, obtains To faint yellow solid powder 6.2g, as compound shown in Formula VII, yield 97.7%.

5) under nitrogen protection, compound shown in Formula VII (0.132g, 0.5mmol), 2,6-DIPA (0.265g, 1.5mmol), Iron dichloride tetrahydrate (0.090g, 0.45mmol), 10ml glacial acetic acid are added to 25ml round-bottomed flask Middle reflux 6h is removed under reduced pressure solvent and 50ml anhydrous ether is added, a large amount of blue precipitates are precipitated.It is dried to obtain blue powder 0.204g, as compound Fe-3 shown in Formulas I, yield 63.8%.

Structural identification data is as follows:

Compound obtained by formula III:¹H-NMR(400MHz；CDCl₃；TMS):δ7.71(m,2H,Py),2.96(m,2H,- CH₂-),2.82(m,2H,-CH₂-),1.93(m,4H,2x-CH₂-).¹³C NMR(100MHz；CDCl₃；TMS):δ202.8, 154.1,138.9,138.3,129.8,123.4,116.6,40.4,31.4,25.0,21.7.

Compound obtained by formula IV:¹H-NMR(400MHz；CDCl₃；TMS): δ 7.54 (m, 2H, Py), 4.10 (t, J= 3.0Hz,2H,-CH₂), 3.95 (t, J=2.7Hz, 2H ,-CH₂-),3.03(m,2H,-CH₂-),2.04(m,4H,2x-CH₂-), 1.70(m,2H,-CH₂-).¹³C NMR(100MHz；CDCl₃；TMS):δ161.5,141.7,138.9,129.7,128.1, 117.6,109.5,64.9,36.3,34.5,27.1,25.5.

Compound obtained by Formula V:¹H-NMR(400MHz；CDCl₃；TMS): δ 8.26 (m, 2H, Py), 7.93 (d, J=6.2Hz, 1H, Ph), 7.63 (d, J=6.2Hz, 1H, Ph), 7.57 (m, 1H, Ph), 7.46 (m, 2H, Ph), 4.07 (t, J=2.6Hz, 2H,-CH₂), 3.96 (t, J=2.7Hz, 2H ,-CH₂-),3.04(m,2H,-CH₂-),2.09-2.03(m,4H,2x-CH₂-), 1.75(m,2H,-CH₂-).¹³C NMR(100MHz；CDCl₃；TMS):δ192.8,158.1,151.3,140.1,139.3, 136.9,132.6,131.4,127.8,124.0,110.0,64.8,36.7,34.4,27.3,25.5.

Compound obtained by Formula VII:¹H-NMR(400MHz；CDCl₃；TMS): δ 8.24 (m, 2H, Py), 8.10 (d, J= 6.3Hz, 1H, Ph), 7.79 (d, J=6.3Hz, 1H, Ph), 7.60 (m, 1H, Ph), 7.50 (m, 2H, Ph), 3.01 (t, J= 4.6Hz,2H,-CH₂), 2.83 (t, J=4.6Hz, 2H ,-CH₂-),2.00-1.92(m,4H,2x-CH₂-).¹³CNMR (100MHz；CDCl₃；TMS):δ204.1,192.2,154.5,153.8,138.9,138.3,136.0,133.1,131.5, 128.2,126.3,40.7,31.4,25.2,21.9.

Complex obtained by step 5): FT-IR (KBr, cm^-1):3059.2(w),2963.9(m),2923.4(m),2866.1 (m),1591.6(ν_C=N,m),1565.1(m),1462.6(m),1440.7(m),1383.5(w),1361.2(w),1322.8 (m), 1274.8(m),1186.6(m),1116.9(m),1051.2(w),1006.2(m),940.1(w),886.2(w), 842.1 (w), 769.7 (s), 704.4 (vs) elemental analysis C₄₁H₄₉Cl₂FeN₃, theoretical value: C, 69.30, H, 6.95, N, 5.91； Experiment value: C, 69.12, H, 6.89, N, 6.96.

By above structure confirmation data it is found that prepared compound is really target product Fe-3.

Embodiment 2, preparation (E)-N- (((E) -9- (2,6- dimethylaniline) -6,7,8,9- tetrahydro cycloheptane and pyridine - 2- benzyl enamine closes frerrous chloride [Fe-1:Ar³=Ph；Ar¹And Ar²In: R¹=Me, R²=H, R³=H, R⁴=H, R⁵=Me, M= Fe,X¹=X²=Cl]

Using method same as Example 1, only the 2,6-DIPA in step 5) described in embodiment 1 is replaced At 2,6- dimethylaniline, 0.235g blue powder is obtained, the Fe-1 of Formulas I, yield 87.3% are as belonged to.

Structural identification data is as follows: FT-IR (KBr, cm^-1):2918.6(m),2860.2(m),1599.1(ν_C=N,m), 1570.2(m),1545.5(m),1462.2(m),1442.9(m),1376.8(w),1320.7(w),1259.8(m),1268.9 (m),1232.2(w),1203.1(s),1162.2(w),1116.1(m),1087.2(m),1006.8(m),967.2(w), 922.6 (w), 879.9 (w), 837.5 (w), 755.1 (vs), 702.5 (s) elemental analysis C₃₃H₃₃Cl₂FeN₃, theoretical value: C, 66.24,H,5.56,N,7.02；Experiment value: C, 66.26, H, 5.54, N, 6.84.

By above structure confirmation data it is found that prepared compound is really target product Fe-1.

Embodiment 3, preparation (E)-N- (((E) -9- (2,6- diethylaniline) -6,7,8,9- tetrahydro cycloheptane and pyridine - 2- benzyl enamine closes frerrous chloride [Fe-2:Ar³=Ph；Ar¹And Ar²In: R¹=Et, R²=H, R³=H, R⁴=H, R⁵=Et, M= Fe,X¹=X²=Cl]:

Using method same as Example 1, only the 2,6-DIPA in step 5) described in embodiment 1 is replaced At 2,6- diethylaniline, 0.203g blue powder is obtained, the Fe-2 of Formulas I, yield 69.0% are as belonged to.

Structural identification data is as follows: FT-IR (KBr, cm^-1):3032.4(w),2965.9(m),2932.7(m),2870.6 (m),1594.4(ν_C=N,m),1559.6(m),1444.3(s),1324.1(m),1270.4(s),1193.0(m),1112.0 (m), 1035.7 (m), 1002.4 (w), 963.8 (w), 859.9 (w), 771.0 (s), 701.6 (vs) elemental analyses C₃₇H₄₁Cl₂FeN₃, theoretical value: C, 67.90, H, 6.31, N, 6.42；Experiment value: C, 67.50, H, 6.25, N, 6.32.

By above structure confirmation data it is found that prepared compound is really target product Fe-2.

Embodiment 4, preparation (E)-N- (((E) -9- (2,4,6- trimethylaniline) -6,7,8,9- tetrahydro cycloheptane and pyrrole Pyridine -2- benzyl enamine closes frerrous chloride [Fe-4:Ar³=Ph；Ar¹And Ar²In: R¹=Me, R²=H, R³=Me, R⁴=H, R⁵= Me, M=Fe, X¹=X²=Cl]:

Using method same as Example 1, only the 2,6-DIPA in step 5) described in embodiment 1 is replaced At 2,4,6- trimethylanilines, 0.245g blue powder is obtained, the Fe-4 of Formulas I, yield 87.0% are as belonged to.

Structural identification data is as follows: FT-IR (KBr, cm^-1):2916.3(m),2862.7(m),1597.2(ν_C=N,m), 1561.4(m),1474.5(m),1445.4(s),1378.6(m),1306.4(w),1264.3(m),1212.5(m),1154.5 (w), 1114.3 (m), 1035.0 (w), 1008.2 (m), 922.4 (w), 733.6 (w), 701.0 (vs) elemental analyses C₃₅H₃₇Cl₂FeN₃, theoretical value: C, 67.11, H, 5.95, N, 6.71；Experiment value: C, 66.82, H, 5.95, N, 6.48.

By above structure confirmation data it is found that prepared compound is really target product Fe-4.

Embodiment 5, preparation (E)-N- (((E) -9- (2,6- diethyl -4- methylaniline) -6,7,8,9- tetrahydro cycloheptane And pyridine -2- benzyl enamine closes frerrous chloride [Fe-5:Ar³=Ph；Ar¹And Ar²In: R¹=Et, R²=H, R³=Me, R⁴=H, R⁵ =Et, M=Fe, X¹=X²=Cl]:

Using method same as Example 1, only the 2,6-DIPA in step 5 described in embodiment 1 is replaced At 2,6- diethyl -4- methylaniline, 0.210g blue powder is obtained, the Fe-5 of Formulas I, yield 68.4% are as belonged to.

Structural identification data is as follows: FT-IR (KBr, cm^-1):2964.0(m),2931.7(m),2869.9(m),1594.4 (ν_C=N,m),1560.3(m),1454.9(s),1376.3(w),1325.4(m),1208.2(m),1152.8(w),1112.7 (m), 1075.5 (w), 1003.5 (w), 858.5 (s), 785.2 (w), 701.1 (vs) elemental analysis C₃₉H₄₅Cl₂FeN₃, theoretical Value: C, 68.63, H, 6.65, N, 6.16；Experiment value: C, 68.24, H, 6.62, N, 5.94.

By above structure confirmation data it is found that prepared compound is really target product Fe-5.

Embodiment 6, preparation (E)-N- (((E) -9- (2,6- difluoro) -6,7,8,9- tetrahydro cycloheptane and pyridine -2- benzyl Enamine closes frerrous chloride [Fe-6:Ar³=Ph；Ar¹And Ar²In: R¹=F, R²=H, R³=H, R⁴=H, R⁵=F, M=Fe, X¹= X²=Cl]:

Using method same as Example 1, only the 2,6-DIPA in step 5) described in embodiment 1 is replaced At 2,6- difluoroaniline, 0.225g blue powder is obtained, the Fe-6 of Formulas I, yield 73.3% are as belonged to.

Structural identification data is as follows: FT-IR (KBr, cm^-1):2920.3(m),2861.2(m),1601.3(ν_C=N,m), 1570.3(m),1546.5(m),1463.3(m),1446.2(m),1372.0(w),1259.8(m),1269.9(m),1232.5 (w),1204.0(s),1162.2(w),1116.0(m),1088.0(m),967.2(w),923.6(w),878.0(w),837.5 (w), 755.1 (vs), 704.0 (s) elemental analysis C₂₉H₂₁Cl₂F₄FeN₃, theoretical value: C, 56.71, H, 3.45, N, 6.84；It is real Test value: C, 56.26, H, 3.54, N, 6.84.

By above structure confirmation data it is found that prepared compound is really target product Fe-6.

Embodiment 7, preparation (E)-N- (((E) -9- (2,6- dichloroaniline) -6,7,8,9- tetrahydro cycloheptane and pyridine -2- Benzyl enamine closes frerrous chloride [Fe-7:Ar³=Ph；Ar¹And Ar²In: R¹=Cl, R²=H, R³=H, R⁴=H, R⁵=Cl, M= Fe,X¹=X²=Cl]:

Using method same as Example 1, only the 2,6-DIPA in step 5) described in embodiment 1 is replaced At 2,6-DCA, 0.303g blue powder is obtained, the Fe-7 of Formulas I, yield 89.1% are as belonged to.

Structural identification data is as follows: FT-IR (KBr, cm^-1):2966.0(m),2933.1(m),2871.2(m),1595.9 (ν_C=N,m),1559.6(m),1444.4(s),1324.1(m),1271.4(s),1112.1(m),1036.1(m),1002.2 (w), 963.8 (w), 859.5 (w), 771.0 (s), 703.0 (vs) elemental analysis C₂₉H₂₁Cl₆FeN₃, theoretical value: C, 51.22, H,3.11,N,6.18；Experiment value: C, 52.00, H, 3.09, N, 6.12.

By above structure confirmation data it is found that prepared compound is really target product Fe-7.

Embodiment 8, preparation (E)-N- (((E) -9- (2,6- dibromo aniline) -6,7,8,9- tetrahydro cycloheptane and pyridine -2- Benzyl enamine closes frerrous chloride [Fe-8:Ar³=Ph；Ar¹And Ar²In: R¹=Br, R²=H, R³=H, R⁴=H, R⁵=Br, M= Fe, X¹=X²=Cl]:

Using method same as Example 1, only the 2,6-DIPA in step 5) described in embodiment 1 is replaced At 2,6- dibromo aniline, 0.345g blue powder is obtained, the Fe-8 of Formulas I, yield 80.4% are as belonged to.

Structural identification data is as follows: FT-IR (KBr, cm^-1):2916.5(m),2861.7(m),1598.2(ν_C=N,m), 1562.0(m),1445.6(s),1379.1(m),1306.5(w),1212.2(m),1154.5(w),1114.4(m),1035.3 (w), 1009.0 (m), 922.4 (w), 733.6 (w), 703.0 (vs) elemental analysis C₂₉H₂₁Br₄Cl₂FeN₃, theoretical value: C, 40.60,H,2.47,N,4.90；Experiment value: C, 40.32, H, 2.43, N, 4.79.

By above structure confirmation data it is found that prepared compound is really target product Fe-8.

Embodiment 9, ((- 6,7,8,9- tetrahydro cycloheptane is simultaneously by (E) -9- [2,6- bis- (benzhydryl) aniline] by preparation (E)-N- Pyridine -2- benzyl enamine closes frerrous chloride [Fe-9:Ar³=Ph；Ar¹And Ar²In: R¹=Ph₂CH,R²=H, R³=Me, R⁴=H, R⁵=Ph₂CH, M=Fe, X¹=X²=Cl]:

Using method same as Example 1, only the 2,6-DIPA in step 5) described in embodiment 1 is replaced At 2,6- bis- (benzhydryl) aniline, 0.410g blue powder is obtained, the Fe-9 of Formulas I, yield 67.9% are as belonged to.

Structural identification data is as follows: FT-IR (KBr, cm^-1):2970.0(m),2932.7(m),2869.3(m),1595.4 (ν_C=N,m),1561.3(m),1455.5(s),1325.4(m),1208.1(m),1153.0(w),1112.3(m),1076.5 (w), 1002.1 (w), 858.5 (s), 786.2 (w), 702.0 (vs) elemental analysis C₈₁H₆₅Cl₂FeN₃, theoretical value: C, 80.59, H,5.43,N,3.48；Experiment value: C, 80.24, H, 5.45, N, 3.41.

By above structure confirmation data it is found that prepared compound is really target product Fe-9.

Embodiment 10, preparation (E)-N- (((E) -9- (2,6- dimethylaniline) -6,7,8,9- tetrahydro cycloheptane and pyridine - 2- benzyl enamine closes cobalt chloride [Co-1:Ar³=Ph；Ar¹And Ar²In: R¹=Me, R²=H, R³=H, R⁴=H, R⁵=Me, M= Co,X¹=X²=Cl]:

Using method same as Example 1, only the 2,6-DIPA in step 5) described in embodiment 1 is replaced At 2,6- dimethylaniline, Iron dichloride tetrahydrate is substituted for cobalt chloride, obtains 0.246g brownish-yellow powder, as ownership Formulas I Co-1, yield 91.0%.

Structural identification data is as follows: FT-IR (KBr, cm^-1):2973.8(w),2937.4(m),2918.3(m),2860.8 (m),1608.4(ν_C=N,m),1596.6(m),1555.1(m),1464.4(m),1446.9(m),1376.6(w),1322.2 (w),1262.2(s),1231.0(w),1202.8(m),1161.8(w),1117.7(m),1088.8(m),1008.2(m), 967.6 (w), 922.8 (w), 876.3 (w), 838.2 (w), 765.0 (vs), 702.2 (s), 671.7 (w) elemental analyses C₃₃H₃₃Cl₂CoN₃, theoretical value: C, 65.90, H, 5.53, N, 6.99；Experiment value: C, 65.63, H, 5.60, N, 6.96.

By above structure confirmation data it is found that prepared complex is really target product Co-1.

Embodiment 11, preparation (E)-N- (((E) -9- (2,6- diethylaniline) -6,7,8,9- tetrahydro cycloheptane and pyridine - 2- benzyl enamine closes cobalt chloride [Co-2:Ar³=Ph；Ar¹And Ar²In: R¹=Et, R²=H, R³=H, R⁴=H, R⁵=Et, M= Co,X¹=X²=Cl]:

Using method same as Example 1, only the 2,6-DIPA in step 5) described in embodiment 1 is replaced At 2,6- diethylaniline, Iron dichloride tetrahydrate is substituted for cobalt chloride, obtains 0.215g brownish-yellow powder, as ownership Formulas I Co-2, yield 72.7%.

Structural identification data is as follows: FT-IR (KBr, cm^-1):3060.7(w),2964.3(m),2932.5(m),2870.8 (w),1597.2(ν_C=N,m),1565.6(s),1446.8(vs),1374.9(w),1324.9(w),1263.3(vs),1194.2 (m), 1113.9 (s), 1006.7 (m), 967.5 (w), 862.9 (w), 801.8 (m), 772.4 (s) elemental analyses C₃₇H₄₁Cl₂CoN₃, theoretical value: C, 67.58, H, 6.28, N, 6.39；Experiment value: C, 67.29, H, 6.10, N, 6.29.

By above structure confirmation data it is found that prepared complex is really target product Co-2.

Embodiment 12, preparation (E)-N- (((E) -9- (2,6- diisopropyl aniline) -6,7,8,9- tetrahydro cycloheptane and pyrrole Pyridine -2- benzyl enamine closes cobalt chloride [Co-3:Ar³=Ph；Ar¹And Ar²In: R¹=i-Pr, R²=H, R³=H, R⁴=H, R⁵=i- Pr, M=Co, X¹=X²=Cl]:

Using method same as Example 1, only the Iron dichloride tetrahydrate in step 5) described in embodiment 1 is substituted for Cobalt chloride obtains 0.180g brownish-yellow powder, as belongs to the Co-3 of Formulas I, yield 56.0%.

Structural identification data is as follows: crystal structure schematic diagram is as shown in Figure 1.Angle between pyridine ring and aniline as seen from the figure Spend near normal.

FT-IR(KBr,cm^-1):3059.7(w),2963.7(s),2866.3(m),1571.1(ν_C=N,m),1462.1 (m),1442.1(m),1383.1(w),1266.2(s),1186.4(w),1116.1(m),1051.9(w),1009.2(w), 941.1 (w), 844.6 (w), 769.0 (vs) elemental analysis C₄₁H₄₉Cl₂CoN₃, theoretical value: C, 69.00, H, 6.92, N, 5.89； Experiment value: C, 68.53, H, 6.94, N, 5.72.

By above structure confirmation data it is found that prepared complex is really target product Co-3.

Embodiment 13, preparation (E)-N- (((E) -9- (2,4,6- trimethylaniline) -6,7,8,9- tetrahydro cycloheptane and pyrrole Pyridine -2- benzyl enamine closes cobalt chloride [Co-4:Ar³=Ph；Ar¹And Ar²In: R¹=Me, R²=H, R³=Me, R⁴=H, R⁵=Me, M =Co, X¹=X²=Cl]:

Using method same as Example 1, only the 2,6-DIPA in step 5) described in embodiment 1 is replaced At 2,4,6- trimethylanilines, Iron dichloride tetrahydrate is substituted for cobalt chloride, obtains 0.213g brownish-yellow powder, as ownership formula The Co-4 of I, yield 75.3%.

Structural identification data is as follows: FT-IR (KBr, cm^-1):3001.9(w),2916.6(m),2861.8(m),1601.4 (ν_C=N,m),1559.8(m),1473.8(m),1447.2(s),1378.6(w),1305.9(w),1263.6(s),1214.1 (m),1180.2(w),1156.5(w),1114.9(m),1033.7(w),1008.6(m),952.0(w),854.9(s),786.0 (w), 701.9 (vs) elemental analysis C₃₅H₃₇Cl₂CoN₃, theoretical value: C, 66.78, H, 5.92, N, 6.67；Experiment value: C, 66.31,H,5.82,N,6.58.

By above structure confirmation data it is found that prepared complex is really target product Co-4.

Embodiment 14, preparation (E)-N- (((E) -9- (2,6- diethyl -4- methylaniline) -6,7,8,9- tetrahydro cycloheptane And pyridine -2- benzyl enamine closes cobalt chloride [Co-5:Ar³=Ph；Ar¹And Ar²In: R¹=Et, R²=H, R³=Me, R⁴=H, R⁵= Et, M=Co, X¹=X²=Cl]:

Using method same as Example 1, only the 2,6-DIPA in step 5) described in embodiment 1 is replaced At 2,6- diethyl -4- methylaniline, Iron dichloride tetrahydrate is substituted for cobalt chloride, obtains 0.124g brownish-yellow powder, as Belong to the Co-5 of Formulas I, yield 40.3%.

Structural identification data is as follows: FT-IR (KBr, cm^-1):3024.3(w),2962.0(m),2931.1(m),2869.8 (m),1599.0(ν_C=N,m),1563.7(m),1454.9(vs),1374.2(w),1328.4(w),1264.6(s),1209.7 (m),1180.3(w),1154.9(w),1114.9(m),1077.1(w),1035.5(w),1007.0(m),971.8(w), 857.2 (s), 790.4 (m), 702.5 (vs) elemental analysis C₃₉H₄₅Cl₂CoN₃, theoretical value: C, 68.32, H, 6.62, N, 6.13； Experiment value: C, 68.07, H, 6.50, N, 5.97.

By above structure confirmation data it is found that prepared complex is really target product Co-5.

Embodiment 15, preparation (E)-N- (((E) -9- (2,6- difluoro) -6,7,8,9- tetrahydro cycloheptane and pyridine -2- benzyl Enamine closes cobalt chloride [Co-6:Ar³=Ph；Ar¹And Ar²In: R¹=F, R²=H, R³=H, R⁴=H, R⁵=F, M=Co, X¹=X² =Cl]:

Using method same as Example 1, only the 2,6-DIPA in step 5) described in embodiment 1 is replaced At 2,6- difluoroaniline, Iron dichloride tetrahydrate is substituted for cobalt chloride, obtains 0.220g brown ceramic powder, as belongs to the Co- of Formulas I 6, yield 71.3%.

Structural identification data is as follows: FT-IR (KBr, cm^-1):2921.3(m),2861.5(m),1600.4(ν_C=N,m), 1572.0(m),1546.5(m),1463.5(m),1372.5(w),1260.1(m),1232.5(w),1204.1(s),1163.2 (w),1114.1(m),1089.5(m),967.5(w),923.9(w),878.8(w),837.4(w),755.0(vs),702.4 (s) elemental analysis C₂₉H₂₁Cl₂F₄FeN₃, theoretical value: C, 56.42, H, 3.43, N, 6.81；Experiment value: C, 56.01, H, 3.24, N,6.77。

By above structure confirmation data it is found that prepared compound is really target product Co-6.

Embodiment 16, preparation (E)-N- (((E) -9- (2,6- dichloroaniline) -6,7,8,9- tetrahydro cycloheptane and pyridine -2- Benzyl enamine closes cobalt chloride [Co-7:Ar³=Ph；Ar¹And Ar²In: R¹=Cl, R²=H, R³=H, R⁴=H, R⁵=Cl, M=Co, X¹=X²=Cl]:

Using method same as Example 1, only the 2,6-DIPA in step 5) described in embodiment 1 is replaced At 2,6-DCA, Iron dichloride tetrahydrate is substituted for cobalt chloride, obtains 0.295g brown ceramic powder, as belongs to the Co- of Formulas I 7, yield 86.4%.

Structural identification data is as follows: FT-IR (KBr, cm^-1):2965.5(m),2932.3(m),2872.2(m),1596.9 (ν_C=N,m),1560.1(m),1444.3(s),1323.5(m),1271.2(s),1112.2(m),1036.0(m),1002.3 (w), 964.0 (w), 859.6 (w), 770.1 (s), 702.5 (vs) elemental analysis C₂₉H₂₁Cl₆CoN₃, theoretical value: C, 50.99, H,3.10,N,6.15；Experiment value: C, 50.54, H, 3.08, N, 6.10.

By above structure confirmation data it is found that prepared compound is really target product Co-7.

Embodiment 17, preparation (E)-N- (((E) -9- (2,6- dibromo aniline) -6,7,8,9- tetrahydro cycloheptane and pyridine -2- Benzyl enamine closes cobalt chloride [Co-8:Ar³=Ph；Ar¹And Ar²In: R¹=Br, R²=H, R³=H, R⁴=H, R⁵=Br, M=Co, X¹=X²=Cl]:

Using method same as Example 1, only the 2,6-DIPA in step 5) described in embodiment 1 is replaced At 2,6- dibromo aniline, Iron dichloride tetrahydrate is substituted for cobalt chloride, obtains 0.361g brown ceramic powder, as belongs to the Co- of Formulas I 8, yield 83.9%.

Structural identification data is as follows: FT-IR (KBr, cm^-1):2920.5(m),2862.1(m),1599.1(ν_C=N,m), 1563.0(m),1445.4(s),1378.1(m),1212.1(m),1155.5(w),1112.3(m),1035.4(w),1009.2 (m), 923.4 (w), 733.8 (w), 702.3 (vs) elemental analysis C₂₉H₂₁Br₄Cl₂CoN₃, theoretical value: C, 40.46, H, 2.46, N,4.88；Experiment value: C, 40.23, H, 2.45, N, 4.61.

By above structure confirmation data it is found that prepared compound is really target product Co-8.

Embodiment 18, ((- 6,7,8,9- tetrahydro cycloheptane is simultaneously by (E) -9- (bis- benzhydryl aniline of 2,6-) by preparation (E)-N- Pyridine -2- benzyl enamine closes cobalt chloride [Co-9:Ar³=Ph；Ar¹And Ar²In: R¹=Ph₂CH,R²=H, R³=Me, R⁴=H, R⁵ =Ph₂CH, M=Co, X¹=X²=Cl]:

Using method same as Example 1, only the 2,6-DIPA in step 5) described in embodiment 1 is replaced At 2,6-, bis- benzhydryl aniline, Iron dichloride tetrahydrate is substituted for cobalt chloride, obtains 0.422g brown ceramic powder, as ownership formula The Co-9 of I, yield 69.8%.

Structural identification data is as follows: FT-IR (KBr, cm^-1):2971.1(m),2930.1(m),2869.3(m),1598.0 (ν_C=N,m),1562.3(m),1456.0(s),1326.2(m),1208.4(m),1153.2(w),1111.1(m),1076.8 (w), 1002.3 (w), 859.5 (s), 786.3 (w), 703.1 (vs) elemental analysis C₈₁H₆₅Cl₂CoN₃, theoretical value: C, 80.39, H,5.41,N,3.47；Experiment value: C, 80.01, H, 5.38, N, 3.43.

By above structure confirmation data it is found that prepared compound is really target product Co-9.

Embodiment 19 combines the vinyl polymerization being catalyzed under normal pressure using complex Fe-3 and MAO:

A) under nitrogen protection, 50ml has been dissolved to the toluene solution of complex Fe-3 and the co-catalyst MAO of 4.1ml The toluene solution and 50ml toluene of (1.46mol/L) are added sequentially in 250ml reaction kettle.At this point, mechanical stirring starts, protect 400 revs/min are held, when temperature reaches 0 DEG C, ethylene is filled with into reaction kettle, polymerization reaction starts.Keep 1atm's at 0 DEG C Ethylene pressure stirs 30min.The ethanol solution neutralization reaction liquid being acidified with 5% hydrochloric acid of mass fraction obtains polymer precipitating, It is washed for several times with ethyl alcohol, vacuum drying to constant weight.Polymerization activity: 1.14 × 10⁶g/mol(Fe)h^-1。

B) substantially it is same a), difference is: polymerization temperature be 10 DEG C.Co-catalyst dosage is the MAO (1.46mol/ of 2.1ml L toluene solution), makes Al/Fe=1000:1.Polymerization activity: 0.74 × 10⁶g/mol(Fe)h^-1。

C) substantially it is same a), difference is: polymerization temperature be 10 DEG C.Co-catalyst dosage is the MAO (1.46mol/ of 3.1ml L toluene solution), makes Al/Fe=1500:1.Polymerization activity: 0.91 × 10⁶g/mol(Fe)h^-1。

D) substantially it is same a), difference is: polymerization temperature be 10 DEG C.Co-catalyst dosage is the MAO (1.46mol/ of 5.1ml L toluene solution), makes Al/Fe=2500:1.Polymerization activity: 1.06 × 10⁶g/mol(Fe)h^-1。

E) substantially it is same a), difference is: polymerization temperature be 10 DEG C.Co-catalyst dosage is the MAO (1.46mol/ of 6.2ml L toluene solution), makes Al/Fe=3000:1.Polymerization activity: 0.79 × 10⁶g/mol(Fe)h^-1。

F) substantially it is same a), difference is: polymerization temperature be 10 DEG C.Co-catalyst dosage is the MAO (1.46mol/ of 7.2ml L toluene solution), makes Al/Fe=3500:1.Polymerization activity: 1.24 × 10⁶g/mol(Fe)h^-1。

G) substantially it is same a), difference is: polymerization temperature be 20 DEG C.Co-catalyst dosage is the MAO (1.46mol/ of 4.1ml L toluene solution), makes Al/Fe=2000:1.Polymerization activity: 0.75 × 10⁶g/mol(Fe)h^-1。

H) substantially it is same a), difference is: polymerization temperature be 30 DEG C.Co-catalyst dosage is the MAO (1.46mol/ of 4.1ml L toluene solution), makes Al/Fe=2000:1.Polymerization activity: 0.62 × 10⁶g/mol(Fe)h^-1。

Embodiment 20 combines the vinyl polymerization being catalyzed under normal pressure using complex Fe-1 and MAO:

Substantially with a), difference is: major catalyst Fe-1 in embodiment 19；Co-catalyst dosage is the MAO of 5.1ml The toluene solution of (1.46mol/L), makes Al/Fe=2500:1, and polymerization temperature is 10 DEG C.Polymerization activity: 2.59 × 10⁶g/mol (Fe)h^-1。

Embodiment 21 combines the vinyl polymerization being catalyzed under normal pressure using complex Fe-2 and MAO:

Substantially with a), difference is: major catalyst Fe-2 in embodiment 19；Co-catalyst dosage is the MAO of 5.1ml The toluene solution of (1.46mol/L), makes Al/Fe=2500:1, and polymerization temperature is 10 DEG C.Polymerization activity: 2.57 × 10⁶g/mol (Fe)h^-1。

Embodiment 22 combines the vinyl polymerization being catalyzed under normal pressure using complex Fe-4 and MAO:

Substantially with a), difference is: major catalyst Fe-4 in embodiment 19；Co-catalyst dosage is the MAO of 5.1ml The toluene solution of (1.46mol/L), makes Al/Fe=2500:1, and polymerization temperature is 10 DEG C.Polymerization activity: 2.26 × 10⁶g/mol (Fe)h^-1。

Embodiment 23 combines the vinyl polymerization being catalyzed under normal pressure using complex Fe-5 and MAO:

Substantially with a), difference is: major catalyst Fe-5 in embodiment 19；Co-catalyst dosage is the MAO of 5.1ml The toluene solution of (1.46mol/L), makes Al/Fe=2500:1, and polymerization temperature is 10 DEG C.Polymerization activity: 2.20 × 10⁶g/mol (Fe)h^-1。

Embodiment 24 combines the vinyl polymerization being catalyzed under normal pressure using complex Fe-6 and MAO:

Substantially with a), difference is: major catalyst Fe-6 in embodiment 19；Co-catalyst dosage is the MAO of 5.1ml The toluene solution of (1.46mol/L), makes Al/Fe=2500:1, and polymerization temperature is 10 DEG C.Polymerization activity: 2.90 × 10⁶g/mol (Fe)h^-1。

Embodiment 25 combines the vinyl polymerization being catalyzed under normal pressure using complex Fe-7 and MAO:

Substantially with a), difference is: major catalyst Fe-7 in embodiment 19；Co-catalyst dosage is the MAO of 5.1ml The toluene solution of (1.46mol/L), makes Al/Fe=2500:1, and polymerization temperature is 10 DEG C.Polymerization activity: 2.61 × 10⁶g/mol (Fe)h^-1。

Embodiment 27 combines the vinyl polymerization being catalyzed under normal pressure using complex Fe-8 and MAO:

Substantially with a), difference is: major catalyst Fe-8 in embodiment 19；Co-catalyst dosage is the MAO of 5.1ml The toluene solution of (1.46mol/L), makes Al/Fe=2500:1, and polymerization temperature is 10 DEG C.Polymerization activity: 2.01 × 10⁶g/mol (Fe)h^-1。

Embodiment 28 combines the vinyl polymerization being catalyzed under normal pressure using complex Fe-9 and MAO:

Substantially with a), difference is: major catalyst Fe-9 in embodiment 19；Co-catalyst dosage is the MAO of 5.1ml The toluene solution of (1.46mol/L), makes Al/Fe=2500:1, and polymerization temperature is 10 DEG C.Polymerization activity: 1.89 × 10⁶g/mol (Fe)h^-1。

Embodiment 29 combines the vinyl polymerization being catalyzed under pressurization using complex Fe-3 and MAO:

Substantially with a), difference is in embodiment 19: polymerization temperature is 40 DEG C.Ethylene pressure is 10atm.Polymerization activity: 4.15×10⁶g/mol(Fe)h^-1。

Substantially with a), difference is in embodiment 19: polymerization temperature is 50 DEG C, polymerization pressure 10atm.Polymerization activity: 11.57×10⁶g/mol(Fe)h^-1。

Substantially with a), difference is in embodiment 11: polymerization temperature is 60 DEG C, polymerization pressure 10atm.Polymerization activity: 12.17×10⁶g/mol(Fe)h^-1。

Substantially with a), difference is in embodiment 19: polymerization temperature is 70 DEG C, polymerization pressure 10atm.Polymerization activity: 8.26×10⁶g/mol(Fe)h^-1。

Substantially with a), difference is in embodiment 19: polymerization temperature is 80 DEG C, polymerization pressure 10atm.Polymerization activity: 6.87×10⁶g/mol(Fe)h^-1。

Substantially with a), difference is in embodiment 19: polymerization temperature is 60 DEG C, polymerization pressure 10atm.Co-catalyst is used Amount is the toluene solution of the MAO (1.46mol/L) of 3.1ml, makes Al/Fe=1500:1.Polymerization activity: 9.55 × 10⁶g/mol (Fe)h^-1。

Substantially with a), difference is in embodiment 19: polymerization temperature is 60 DEG C, polymerization pressure 10atm.Co-catalyst is used Amount is the toluene solution of the MAO (1.46mol/L) of 5.1ml, makes Al/Fe=2500:1.Polymerization activity: 13.11 × 10⁶g/mol (Fe)h^-1。

Substantially with a), difference is in embodiment 19: polymerization temperature is 60 DEG C, polymerization pressure 10atm.Co-catalyst is used Amount is the toluene solution of the MAO (1.46mol/L) of 6.2ml, makes Al/Fe=3000:1.Polymerization activity: 10.88 × 10⁶g/mol (Fe)h^-1。

Substantially with a), difference is in embodiment 19: polymerization temperature is 60 DEG C, polymerization pressure 10atm.Co-catalyst is used Amount is the toluene solution of the MAO (1.46mol/L) of 7.2ml, makes Al/Fe=3500:1.Polymerization activity: 10.41 × 10⁶g/mol (Fe)h^-1。

Substantially with a), difference is in embodiment 19: polymerization temperature is 60 DEG C.Polymerization pressure is 5atm.Co-catalyst is used Amount is the toluene solution of the MAO (1.46mol/L) of 5.1ml, makes Al/Fe=2500:1.Polymerization activity: 7.21 × 10⁶g/mol (Fe)h^-1。

Embodiment 30 combines the vinyl polymerization being catalyzed under high pressure using complex Fe-1 and MAO:

Substantially with a), difference is: major catalyst Fe-1 in embodiment 19, co-catalyst dosage is the MAO of 5.1ml The toluene solution of (1.46mol/L) makes Al/Fe=2500:1, and polymerization temperature is 60 DEG C, polymerization pressure 10atm.Polymerization is lived Property: 15.09 × 10⁶g/mol(Fe)h^-1。

Embodiment 31 combines the vinyl polymerization being catalyzed under high pressure using complex Fe-2 and MAO:

Substantially with a), difference is: major catalyst Fe-2 in embodiment 19；Co-catalyst dosage is the MAO of 5.1ml The toluene solution of (1.46mol/L), makes Al/Fe=2500:1, and polymerization temperature is 60 DEG C.Polymerization pressure is 10atm.Polymerization is lived Property: 10.65 × 10⁶g/mol(Fe)h^-1。

Embodiment 32 combines the vinyl polymerization being catalyzed under high pressure using complex Fe-4 and MAO:

Substantially with a), difference is: major catalyst Fe-4 in embodiment 19, co-catalyst dosage is the MAO of 5.1ml The toluene solution of (1.46mol/L) makes Al/Fe=2500:1, and polymerization temperature is 60 DEG C, polymerization pressure 10atm.Polymerization is lived Property: 15.61 × 10⁶g/mol(Fe)h^-1。

Embodiment 33 combines the vinyl polymerization being catalyzed under high pressure using complex Fe-5 and MAO:

Substantially with e), difference is: major catalyst Fe-5 in embodiment 19；Co-catalyst dosage is the MAO of 5.1ml The toluene solution of (1.46mol/L) makes Al/Fe=2500:1, and polymerization temperature is 60 DEG C, polymerization pressure 10atm.Polymerization is lived Property: 12.90 × 10⁶g/mol(Fe)h^-1。

Embodiment 34 combines the vinyl polymerization being catalyzed under high pressure using complex Fe-6 and MAO:

Substantially with a), difference is: major catalyst Fe-6 in embodiment 19, co-catalyst dosage is the MAO of 5.1ml The toluene solution of (1.46mol/L) makes Al/Fe=2500:1, and polymerization temperature is 60 DEG C, polymerization pressure 10atm.Polymerization is lived Property: 15.22 × 10⁶g/mol(Fe)h^-1。

Embodiment 35 combines the vinyl polymerization being catalyzed under high pressure using complex Fe-7 and MAO:

Substantially with a), difference is: major catalyst Fe-7 in embodiment 19；Co-catalyst dosage is the MAO of 5.1ml The toluene solution of (1.46mol/L), makes Al/Fe=2500:1, and polymerization temperature is 60 DEG C.Polymerization pressure is 10atm.Polymerization is lived Property: 10.95 × 10⁶g/mol(Fe)h^-1。

Embodiment 36 combines the vinyl polymerization being catalyzed under high pressure using complex Fe-8 and MAO:

Substantially with a), difference is: major catalyst Fe-8 in embodiment 19, co-catalyst dosage is the MAO of 5.1ml The toluene solution of (1.46mol/L) makes Al/Fe=2500:1, and polymerization temperature is 60 DEG C, polymerization pressure 10atm.Polymerization is lived Property: 15.51 × 10⁶g/mol(Fe)h^-1。

Embodiment 37 combines the vinyl polymerization being catalyzed under high pressure using complex Fe-9 and MAO:

Substantially with e), difference is: major catalyst Fe-9 in embodiment 19；Co-catalyst dosage is the MAO of 5.1ml The toluene solution of (1.46mol/L) makes Al/Fe=2500:1, and polymerization temperature is 60 DEG C, polymerization pressure 10atm.Polymerization is lived Property: 12.02 × 10⁶g/mol(Fe)h^-1。

Embodiment 38 combines the vinyl polymerization being catalyzed under normal pressure using complex Fe-3 and MMAO:

Substantially with a), difference is in embodiment 19: co-catalyst dosage is the toluene of the MMAO (2.0mol/L) of 3.0ml Solution, makes Al/Fe=2000:1, and polymerization temperature is 0 DEG C.Polymerization activity: 1.26 × 10⁶g/mol(Fe)h^-1。

Substantially with a), difference is in embodiment 19: co-catalyst dosage is the toluene of the MMAO (2.0mol/L) of 3.0ml Solution, makes Al/Fe=2000:1, and polymerization temperature is 10 DEG C.Polymerization activity: 1.30 × 10⁶g/mol(Fe)h^-1。

Substantially with a), difference is in embodiment 19: co-catalyst dosage is the toluene of the MMAO (2.0mol/L) of 3.0ml Solution, makes Al/Fe=2000:1, and polymerization temperature is 20 DEG C.Polymerization activity: 1.25 × 10⁶g/mol(Fe)h^-1。

Substantially with a), difference is in embodiment 19: co-catalyst dosage is the toluene of the MMAO (2.0mol/L) of 3.0ml Solution, makes Al/Fe=2000:1, and polymerization temperature is 30 DEG C.Polymerization activity: 1.10 × 10⁶g/mol(Fe)h^-1。

Substantially with a), difference is in embodiment 19: co-catalyst dosage is the toluene of the MMAO (2.0mol/L) of 3.0ml Solution, makes Al/Fe=2000:1, and polymerization temperature is 40 DEG C.Polymerization activity: 0.71 × 10⁶g/mol(Fe)h^-1。

Substantially with a), difference is in embodiment 19: co-catalyst dosage is the toluene of the MMAO (2.0mol/L) of 1.5ml Solution, makes Al/Fe=1000:1, and polymerization temperature is 10 DEG C.Polymerization activity: 0.99 × 10⁶g/mol(Fe)h^-1。

Substantially with a), difference is in embodiment 19: co-catalyst dosage is the toluene of the MMAO (2.0mol/L) of 2.3ml Solution, makes Al/Fe=1500:1, and polymerization temperature is 10 DEG C.Polymerization activity: 1.23 × 10⁶g/mol(Fe)h^-1。

Substantially with a), difference is in embodiment 19: co-catalyst dosage is the toluene of the MMAO (2.0mol/L) of 3.8ml Solution, makes Al/Fe=2500:1, and polymerization temperature is 10 DEG C.Polymerization activity: 1.39 × 10⁶g/mol(Fe)h^-1。

Substantially with a), difference is in embodiment 19: co-catalyst dosage is the toluene of the MMAO (2.0mol/L) of 4.5ml Solution, makes Al/Fe=3000:1, and polymerization temperature is 10 DEG C.Polymerization activity: 1.33 × 10⁶g/mol(Fe)h^-1。

Substantially with a), difference is in embodiment 19: co-catalyst dosage is the toluene of the MMAO (2.0mol/L) of 5.3ml Solution, makes Al/Fe=3500:1, and polymerization temperature is 10 DEG C.Polymerization activity: 1.15 × 10⁶g/mol(Fe)h^-1。

Substantially with a), difference is in embodiment 19: co-catalyst dosage is the toluene of the MMAO (2.0mol/L) of 3.8ml Solution makes Al/Fe=2500:1, and polymerization temperature is 10 DEG C, polymerization time 15min.Polymerization activity: 1.91 × 10⁶g/mol (Fe)h^-1。

Substantially with a), difference is in embodiment 19: co-catalyst dosage is the toluene of the MMAO (2.0mol/L) of 3.8ml Solution makes Al/Fe=2500:1, and polymerization temperature is 10 DEG C, polymerization time 45min.Polymerization activity: 1.01 × 10⁶g/mol (Fe)h^-1。

Substantially with a), difference is in embodiment 19: co-catalyst dosage is the toluene of the MMAO (2.0mol/L) of 3.8ml Solution makes Al/Fe=2500:1, and polymerization temperature is 10 DEG C, polymerization time 60min.Polymerization activity: 0.95 × 10⁶g/mol (Fe)h^-1。

Embodiment 39 combines the vinyl polymerization being catalyzed under normal pressure using complex Fe-1 and MMAO:

Substantially with e), difference is: major catalyst Fe-1 in embodiment 19；Co-catalyst dosage is the MMAO of 3.8ml The toluene solution of (2.0mol/L), makes Al/Fe=2500:1, and polymerization temperature is 10 DEG C.Polymerization activity: 2.64 × 10⁶ g/mol (Fe)h^-1。

Embodiment 40 combines the vinyl polymerization being catalyzed under normal pressure using complex Fe-2 and MMAO:

Substantially with e), difference is: major catalyst Fe-2 in embodiment 19；Co-catalyst dosage is the MMAO of 3.8ml The toluene solution of (2.0mol/L), makes Al/Fe=2500:1, and polymerization temperature is 10 DEG C.Polymerization activity: 2.59 × 10⁶g/mol (Fe)h^-1。

Embodiment 41 combines the vinyl polymerization being catalyzed under normal pressure using complex Fe-4 and MMAO:

Substantially with e), difference is: major catalyst Fe-4 in embodiment 19, co-catalyst dosage is the MMAO of 3.8ml The toluene solution of (2.0mol/L), makes Al/Fe=2500:1, and polymerization temperature is 10 DEG C.Polymerization activity: 2.53 × 10⁶g/mol (Fe)h^-1。

Embodiment 42 combines the vinyl polymerization being catalyzed under normal pressure using complex Fe-5 and MMAO:

Substantially with e), difference is: major catalyst Fe-5 in embodiment 19, co-catalyst dosage is the MMAO of 3.8ml The toluene solution of (2.0mol/L), makes Al/Fe=2500:1, and polymerization temperature is 10 DEG C.Polymerization activity: 2.42 × 10⁶g/mol (Fe)h^-1。

Embodiment 43 combines the vinyl polymerization being catalyzed under normal pressure using complex Fe-6 and MMAO:

Substantially with e), difference is: major catalyst Fe-6 in embodiment 19；Co-catalyst dosage is the MMAO of 3.8ml The toluene solution of (2.0mol/L), makes Al/Fe=2500:1, and polymerization temperature is 10 DEG C.Polymerization activity: 2.85 × 10⁶g/mol (Fe)h^-1。

Embodiment 44 combines the vinyl polymerization being catalyzed under normal pressure using complex Fe-7 and MMAO:

Substantially with e), difference is: major catalyst Fe-7 in embodiment 19；Co-catalyst dosage is the MMAO of 3.8ml The toluene solution of (2.0mol/L), makes Al/Fe=2500:1, and polymerization temperature is 10 DEG C.Polymerization activity: 2.71 × 10⁶g/mol (Fe)h^-1。

Embodiment 45 combines the vinyl polymerization being catalyzed under normal pressure using complex Fe-8 and MMAO:

Substantially with e), difference is: major catalyst Fe-8 in embodiment 19, co-catalyst dosage is the MMAO of 3.8ml The toluene solution of (2.0mol/L), makes Al/Fe=2500:1, and polymerization temperature is 10 DEG C.Polymerization activity: 2.63 × 10⁶g/mol (Fe)h^-1。

Embodiment 46 combines the vinyl polymerization being catalyzed under normal pressure using complex Fe-9 and MMAO:

Substantially with e), difference is: major catalyst Fe-9 in embodiment 19, co-catalyst dosage is the MMAO of 3.8ml The toluene solution of (2.0mol/L), makes Al/Fe=2500:1, and polymerization temperature is 10 DEG C.Polymerization activity: 2.23 × 10⁶g/mol (Fe)h^-1。

Embodiment 47 combines the vinyl polymerization being catalyzed under pressurization using complex Fe-3 and MMAO:

Substantially with a), difference is in embodiment 19: co-catalyst dosage is the toluene of the MMAO (2.0mol/L) of 3.0ml Solution makes Al/Fe=2000:1, and polymerization temperature is 50 DEG C, polymerization pressure 10atm.Polymerization activity: 5.27 × 10⁶g/mol (Fe)h^-1。

Substantially with a), difference is in embodiment 19: co-catalyst dosage is the toluene of the MMAO (2.0mol/L) of 3.0ml Solution makes Al/Fe=2000:1, and polymerization temperature is 60 DEG C, polymerization pressure 10atm.Polymerization activity: 7.04 × 10⁶g/mol (Fe)h^-1。

Substantially with a), difference is in embodiment 19: co-catalyst dosage is the toluene of the MMAO (2.0mol/L) of 3.0ml Solution makes Al/Fe=2000:1, and polymerization temperature is 70 DEG C, polymerization pressure 10atm.Polymerization activity: 10.67 × 10⁶g/mol (Fe)h^-1。

Substantially with a), difference is in embodiment 19: co-catalyst dosage is the toluene of the MMAO (2.0mol/L) of 3.0ml Solution makes Al/Fe=2000:1, and polymerization temperature is 80 DEG C, polymerization pressure 10atm.Polymerization activity: 4.83 × 10⁶g/mol (Fe)h^-1。

Substantially with a), difference is in embodiment 19: co-catalyst dosage is the toluene of the MMAO (2.0mol/L) of 3.0ml Solution makes Al/Fe=2000:1, and polymerization temperature is 90 DEG C, polymerization pressure 10atm.Polymerization activity: 0.36 × 10⁶g/mol (Fe)h^-1。

Substantially with a), difference is in embodiment 19: polymerization temperature is 70 DEG C, polymerization pressure 10atm, and co-catalyst is used Amount is the toluene solution of the MMAO (2.0mol/L) of 1.5ml, makes Al/Fe=1000:1.Polymerization activity: 7.47 × 10⁶g/mol (Fe)h^-1。

Substantially with a), difference is in embodiment 19: polymerization temperature is 70 DEG C, polymerization pressure 10atm, and co-catalyst is used Amount is the toluene solution of the MMAO (2.0mol/L) of 2.3ml, makes Al/Fe=1500:1.Polymerization activity: 8.59 × 10⁶g/mol (Fe)h^-1。

Substantially with a), difference is in embodiment 19: polymerization temperature is 70 DEG C, polymerization pressure 10atm, and co-catalyst is used Amount is the toluene solution of the MMAO (2.0mol/L) of 3.8ml, makes Al/Fe=2500:1.Polymerization activity: 10.24 × 10⁶g/mol (Fe)h^-1。

Substantially with a), difference is in embodiment 19: polymerization temperature is 70 DEG C.Polymerization pressure is 10atm, and co-catalyst is used Amount is the toluene solution of the MMAO (2.0mol/L) of 4.5ml, makes Al/Fe=3000:1.Polymerization activity: 9.33 × 10⁶g/mol (Fe)h^-1。

Substantially with a), difference is in embodiment 19: polymerization temperature is 70 DEG C, polymerization pressure 5atm, and co-catalyst is used Amount is the toluene solution of the MMAO (2.0mol/L) of 3.0ml, makes Al/Fe=2000:1.Polymerization activity: 5.16 × 10⁶g/mol (Fe)h^-1。

Substantially with a), difference is in embodiment 19: co-catalyst dosage is the toluene of the MMAO (2.0mol/L) of 3.0ml Solution makes Al/Fe=2000:1, and polymerization temperature is 70 DEG C, polymerization time 15min.Polymerization activity: 15.52 × 10⁶g/mol (Fe)h^-1。

Substantially with a), difference is in embodiment 19: co-catalyst dosage is the toluene of the MMAO (2.0mol/L) of 3.0ml Solution makes Al/Fe=2000:1, and polymerization temperature is 70 DEG C, polymerization time 45min.Polymerization activity: 8.37 × 10⁶ g/mol (Fe)h^-1。

Substantially with a), difference is in embodiment 19: co-catalyst dosage is the toluene of the MMAO (2.0mol/L) of 3.0ml Solution makes Al/Fe=2000:1, and polymerization temperature is 70 DEG C, polymerization time 60min.Polymerization activity: 6.66 × 10⁶g/mol (Fe)h^-1。

Embodiment 48 combines the vinyl polymerization being catalyzed under high pressure using complex Fe-1 and MMAO:

Substantially with a), difference is: major catalyst Fe-1 in embodiment 19；Co-catalyst dosage is the MMAO of 3.0ml The toluene solution of (2.0mol/L) makes Al/Fe=2000:1, and polymerization temperature is 70 DEG C, polymerization pressure 10atm.Polymerization activity: 11.13×10⁶g/mol(Fe)h^-1。

Embodiment 49 combines the vinyl polymerization being catalyzed under high pressure using complex Fe-2 and MMAO:

Substantially with a), difference is: major catalyst Fe-2 in embodiment 19；Co-catalyst dosage is the MMAO of 3.0ml The toluene solution of (2.0mol/L) makes Al/Fe=2000:1, and polymerization temperature is 70 DEG C, polymerization pressure 10atm.Polymerization activity: 8.77×10⁶g/mol(Fe)h^-1。

Embodiment 50 combines the vinyl polymerization being catalyzed under high pressure using complex Fe-4 and MMAO:

Substantially with a), difference is: major catalyst Fe-4 in embodiment 19, co-catalyst dosage is the MMAO of 3.0ml The toluene solution of (2.0mol/L) makes Al/Fe=2000:1, and polymerization temperature is 70 DEG C, polymerization pressure 10atm.Polymerization activity: 13.36×10⁶g/mol(Fe)h^-1。

Embodiment 51 combines the vinyl polymerization being catalyzed under high pressure using complex Fe-5 and MMAO:

Substantially with a), difference is: major catalyst Fe-5 in embodiment 19, co-catalyst dosage is the MMAO of 3.0ml The toluene solution of (2.0mol/L) makes Al/Fe=2000:1, and polymerization temperature is 70 DEG C, polymerization pressure 10atm.Polymerization activity: 9.17×10⁶g/mol(Fe)h^-1。

Embodiment 52 combines the vinyl polymerization being catalyzed under high pressure using complex Fe-6 and MMAO:

Substantially with a), difference is: major catalyst Fe-6 in embodiment 19；Co-catalyst dosage is the MMAO of 3.0ml The toluene solution of (2.0mol/L) makes Al/Fe=2000:1, and polymerization temperature is 70 DEG C, polymerization pressure 10atm.Polymerization activity: 11.41×10⁶g/mol(Fe)h^-1。

Embodiment 53 combines the vinyl polymerization being catalyzed under high pressure using complex Fe-7 and MMAO:

Substantially with a), difference is: major catalyst Fe-7 in embodiment 19；Co-catalyst dosage is the MMAO of 3.0ml The toluene solution of (2.0mol/L) makes Al/Fe=2000:1, and polymerization temperature is 70 DEG C, polymerization pressure 10atm.Polymerization activity: 8.90×10⁶g/mol(Fe)h^-1。

Embodiment 54 combines the vinyl polymerization being catalyzed under high pressure using complex Fe-8 and MMAO:

Substantially with a), difference is: major catalyst Fe-8 in embodiment 19, co-catalyst dosage is the MMAO of 3.0ml The toluene solution of (2.0mol/L) makes Al/Fe=2000:1, and polymerization temperature is 70 DEG C, polymerization pressure 10atm.Polymerization activity: 13.50×10⁶g/mol(Fe)h^-1。

Embodiment 55 combines the vinyl polymerization being catalyzed under high pressure using complex Fe-9 and MMAO:

Substantially with a), difference is: major catalyst Fe-9 in embodiment 19, co-catalyst dosage is the MMAO of 3.0ml The toluene solution of (2.0mol/L) makes Al/Fe=2000:1, and polymerization temperature is 70 DEG C, polymerization pressure 10atm.Polymerization activity: 8.97×10⁶g/mol(Fe)h^-1。

Embodiment 56 combines the vinyl polymerization being catalyzed under high pressure using complex Co-4 and MMAO

A) under nitrogen protection, the co-catalysis of the toluene solution 50ml and 2.3ml of catalyst Co-4 (3 μm of ol) will have been dissolved The toluene solution and 50ml toluene of agent MMAO (2.0mol/L) is added sequentially in 250ml reactor.Al/Co=at this time 1500:1.Mechanical stirring starts, and is kept for 400 revs/min, when polymerization temperature reaches 50 DEG C, ethylene is filled with into reaction kettle, polymerize Reaction starts.The ethylene pressure that 10atm is kept at 50 DEG C, stirs 30min.With in the ethanol solution of 5% hydrochloric acid acidification and instead Liquid is answered, polymer precipitating is obtained, is washed for several times with ethyl alcohol, vacuum drying to constant weight, polymerization activity: 1.95 × 10⁶g/mol(Co)h^-1。

Substantially it is same a), polymerization temperature be 60 DEG C.Polymerization activity: 2.57 × 10⁶g/mol(Co)h^-1。

Substantially it is same a), polymerization temperature be 70 DEG C.Polymerization activity: 3.43 × 10⁶g/mol(Co)h^-1。

Substantially it is same a), polymerization temperature be 80 DEG C.Polymerization activity: 0.65 × 10⁶g/mol(Co)h^-1。

Substantially it is same a), polymerization temperature be 90 DEG C.Polymerization activity: 0.12 × 10⁶g/mol(Co)h^-1。

Substantially it is same a), difference is: co-catalyst dosage be 1.5ml MMAO (2.0mol/L) toluene solution, Al/Co =1000:1, polymerization temperature are 70 DEG C.Polymerization activity: 2.50 × 10⁶g/mol(Co)h^-1。

Substantially it is same a), difference is: co-catalyst dosage be 3.0ml MMAO (2.0mol/L) toluene solution, Al/Co =2000:1, polymerization temperature are 70 DEG C.Polymerization activity: 2.92 × 10⁶g/mol(Co)h^-1。

Substantially it is same a), difference is: co-catalyst dosage be 3.8ml MMAO (2.0mol/L) toluene solution, Al/Co =2500:1, polymerization temperature are 70 DEG C.Polymerization activity: 2.70 × 10⁶g/mol(Co)h^-1。

Substantially it is same a), difference is: co-catalyst dosage be 4.5ml MMAO (2.0mol/L) toluene solution, Al/Co =3000:1, polymerization temperature are 70 DEG C.Polymerization activity: 2.18 × 10⁶g/mol(Co)h^-1。

Substantially it is same a), difference is: polymerization temperature be 70 DEG C.Polymerization pressure is 5atm.Polymerization activity: 1.87 × 10⁶g/ mol(Co)h^-1。

Embodiment 57 combines the vinyl polymerization being catalyzed under high pressure using complex Co-1 and MMAO

Substantially with a), difference is: major catalyst Co-1 in embodiment 56；Polymerization temperature is 70 DEG C.Polymerization activity: 2.79×10⁶g/mol(Co)h^-1。

Embodiment 58 combines the vinyl polymerization being catalyzed under high pressure using complex Co-2 and MMAO

Substantially with a), difference is: major catalyst Co-2 in embodiment 56；Polymerization temperature is 70 DEG C.Polymerization activity: 2.67×10⁶g/mol(Co)h^-1。

Embodiment 59 combines the vinyl polymerization being catalyzed under high pressure using complex Co-3 and MMAO

Substantially with a), difference is: major catalyst Co-3 in embodiment 56；Polymerization temperature is 70 DEG C.Polymerization activity: 1.18×10⁶g/mol(Co)h^-1。

Embodiment 60 combines the vinyl polymerization being catalyzed under high pressure using complex Co-5 and MMAO

Substantially with a), difference is: major catalyst Co-5 in embodiment 56；Polymerization temperature is 70 DEG C.Polymerization activity: 2.95×10⁶g/mol(Co)h^-1。

Embodiment 61 combines the vinyl polymerization being catalyzed under high pressure using complex Co-6 and MMAO

Substantially with a), difference is: major catalyst Co-6 in embodiment 56；Polymerization temperature is 70 DEG C.Polymerization activity: 2.84×10⁶g/mol(Co)h^-1。

Embodiment 62 combines the vinyl polymerization being catalyzed under high pressure using complex Co-7 and MMAO

Substantially with a), difference is: major catalyst Co-7 in embodiment 56；Polymerization temperature is 70 DEG C.Polymerization activity: 2.71×10⁶g/mol(Co)h^-1。

Embodiment 63 combines the vinyl polymerization being catalyzed under high pressure using complex Co-8 and MMAO

Substantially with a), difference is: major catalyst Co-8 in embodiment 56；Polymerization temperature is 70 DEG C.Polymerization activity: 1.22×10⁶g/mol(Co)h^-1。

Embodiment 64 combines the vinyl polymerization being catalyzed under high pressure using complex Co-9 and MMAO

Substantially with a), difference is: major catalyst Co-9 in embodiment 56；Polymerization temperature is 70 DEG C.Polymerization activity: 2.85×10⁶g/mol(Co)h^-1。

Embodiment 65 combines the vinyl polymerization being catalyzed under high pressure using complex Co-4 and MAO:

Substantially with a), difference is in embodiment 56: polymerization temperature is 40 DEG C.Co-catalyst dosage is the MAO of 3.1ml The toluene solution of (1.46mol/L), makes Al/Co=1500:1.Polymerization activity: 2.56 × 10⁶g/mol(Co)h^-1。

Substantially with a), difference is in embodiment 56: polymerization temperature is 50 DEG C.Co-catalyst dosage is the MAO of 3.1ml The toluene solution of (1.46mol/L), makes Al/Co=1500:1.Polymerization activity: 5.55 × 10⁶g/mol(Co)h^-1。

Substantially with a), difference is in embodiment 56: polymerization temperature is 60 DEG C.Co-catalyst dosage is the MAO of 3.1ml The toluene solution of (1.46mol/L), makes Al/Co=1500:1.Polymerization activity: 6.12 × 10⁶g/mol(Co)h^-1。

Substantially with a), difference is in embodiment 56: polymerization temperature is 70 DEG C.Co-catalyst dosage is the MAO of 3.1ml The toluene solution of (1.46mol/L), makes Al/Co=1500:1.Polymerization activity: 5.30 × 10⁶g/mol(Co)h^-1。

Substantially with a), difference is in embodiment 56: polymerization temperature is 80 DEG C.Co-catalyst dosage is the MAO of 3.1ml The toluene solution of (1.46mol/L), makes Al/Co=1500:1.Polymerization activity: 1.85 × 10⁶g/mol(Co)h^-1。

Substantially with a), difference is in embodiment 56: polymerization temperature is 90 DEG C.Co-catalyst dosage is the MAO of 3.1ml The toluene solution of (1.46mol/L), makes Al/Co=1500:1.Polymerization activity: 0.35 × 10⁶g/mol(Co)h^-1。

Substantially with a), difference is in embodiment 56: co-catalyst dosage is the toluene of the MAO (1.46mol/L) of 2.1ml Solution makes Al/Co=1000:1.Polymerization temperature is 60 DEG C.Polymerization activity: 5.85 × 10⁶g/mol(Co)h^-1。

Substantially with a), difference is in embodiment 56: co-catalyst dosage is the toluene of the MAO (1.46mol/L) of 4.1ml Solution makes Al/Co=2000:1.Polymerization temperature is 60 DEG C.Polymerization activity: 7.24 × 10⁶g/mol(Co)h^-1。

Substantially with a), difference is in embodiment 56: co-catalyst dosage is the toluene of the MAO (1.46mol/L) of 5.1ml Solution makes Al/Co=2500:1.Polymerization temperature is 60 DEG C.Polymerization activity: 8.65 × 10⁶g/mol(Co)h^-1。

Substantially with a), difference is in embodiment 56: co-catalyst dosage is the toluene of the MAO (1.46mol/L) of 6.2ml Solution makes Al/Co=3000:1.Polymerization temperature is 60 DEG C.Polymerization activity: 8.02 × 10⁶g/mol(Co)h^-1。

Substantially with a), difference is in embodiment 56: co-catalyst dosage is the toluene of the MAO (1.46mol/L) of 5.1ml Solution makes Al/Co=2500:1.Polymerization temperature is 60 DEG C.Reaction time is 10min.Polymerization activity: 14.18 × 10⁶g/mol (Co)h^-1。

Substantially with a), difference is in embodiment 56: co-catalyst dosage is the toluene of the MAO (1.46mol/L) of 5.1ml Solution makes Al/Co=2500:1.Polymerization temperature is 60 DEG C.Reaction time is 20min.Polymerization activity: 9.76 × 10⁶g/mol (Co)h^-1。

Substantially with a), difference is in embodiment 56: co-catalyst dosage is the toluene of the MAO (1.46mol/L) of 5.1ml Solution makes Al/Co=2500:1.Polymerization temperature is 60 DEG C.Reaction time is 45min.Polymerization activity: 6.56 × 10⁶g/mol (Co)h^-1。

Substantially with a), difference is in embodiment 56: co-catalyst dosage is the toluene of the MAO (1.46mol/L) of 5.1ml Solution makes Al/Co=2500:1.Polymerization temperature is 60 DEG C.Reaction time is 60min.Polymerization activity: 5.22 × 10⁶g/mol (Co)h^-1。

Substantially with a), difference is in embodiment 56: co-catalyst dosage is the toluene of the MAO (1.46mol/L) of 5.1ml Solution makes Al/Co=2500:1.Polymerization temperature is 60 DEG C.Ethylene atmospheric pressure is 5atm.Polymerization activity: 6.51 × 10⁶g/mol (Co)h^-1。

Embodiment 66 combines the vinyl polymerization being catalyzed under high pressure using complex Co-1 and MAO

Substantially with a), difference is: major catalyst Co-1 in embodiment 56；Co-catalyst dosage is the MAO of 5.1ml The toluene solution of (1.46mol/L), makes Al/Co=2500:1.Polymerization temperature is 60 DEG C.Polymerization activity: 8.15 × 10⁶g/mol (Co)h^-1。

Embodiment 67 combines the vinyl polymerization being catalyzed under high pressure using complex Co-2 and MAO

Substantially with a), difference is: major catalyst Co-2 in embodiment 56；Co-catalyst dosage is the MAO of 5.1ml The toluene solution of (1.46mol/L), makes Al/Co=2500:1.Polymerization temperature is 60 DEG C.Polymerization activity: 6.19 × 10⁶g/mol (Co)h^-1。

Embodiment 68 combines the vinyl polymerization being catalyzed under high pressure using complex Co-3 and MAO

Substantially with a), difference is: major catalyst Co-3 in embodiment 56；Co-catalyst dosage is the MAO of 5.1ml The toluene solution of (1.46mol/L), makes Al/Co=2500:1.Polymerization temperature is 60 DEG C.Polymerization activity: 5.66 × 10⁶g/mol (Co)h^-1。

Embodiment 69 combines the vinyl polymerization being catalyzed under high pressure using complex Co-5 and MAO

Substantially with a), difference is: major catalyst Co-5 in embodiment 56；Co-catalyst dosage is the MAO of 5.1ml The toluene solution of (1.46mol/L), makes Al/Co=2500:1.Polymerization temperature is 60 DEG C.Polymerization activity: 6.38 × 10⁶g/mol (Co)h^-1。

Embodiment 70 combines the vinyl polymerization being catalyzed under high pressure using complex Co-6 and MAO

Substantially with a), difference is: major catalyst Co-6 in embodiment 56；Co-catalyst dosage is the MAO of 5.1ml The toluene solution of (1.46mol/L), makes Al/Co=2500:1.Polymerization temperature is 60 DEG C.Polymerization activity: 8.23 × 10⁶g/mol (Co)h^-1。

Embodiment 71 combines the vinyl polymerization being catalyzed under high pressure using complex Co-7 and MAO

Substantially with a), difference is: major catalyst Co-7 in embodiment 56；Co-catalyst dosage is the MAO of 5.1ml The toluene solution of (1.46mol/L), makes Al/Co=2500:1.Polymerization temperature is 60 DEG C.Polymerization activity: 6.25 × 10⁶g/mol (Co)h^-1。

Embodiment 72 combines the vinyl polymerization being catalyzed under high pressure using complex Co-8 and MAO

Substantially with a), difference is: major catalyst Co-8 in embodiment 56；Co-catalyst dosage is the MAO of 5.1ml The toluene solution of (1.46mol/L), makes Al/Co=2500:1.Polymerization temperature is 60 DEG C.Polymerization activity: 5.80 × 10⁶g/mol (Co)h^-1。

Embodiment 73 combines the vinyl polymerization being catalyzed under high pressure using complex Co-9 and MAO

Substantially with a), difference is: major catalyst Co-9 in embodiment 56；Co-catalyst dosage is the MAO of 5.1ml The toluene solution of (1.46mol/L), makes Al/Co=2500:1.Polymerization temperature is 60 DEG C.Polymerization activity: 6.01 × 10⁶g/mol (Co)h^-1。

Embodiment 74 combines the vinyl polymerization being catalyzed under normal pressure using complex Co-4 and MAO

Substantially with a), difference is in embodiment 56: polymerization temperature is 0 DEG C.Co-catalyst dosage is the MAO of 3.1ml The toluene solution of (1.46mol/L), makes Al/Co=1500:1.Ethylene atmospheric pressure is 1atm.Polymerization activity: 0.86 × 10⁶g/ mol(Co)h^-1。

Substantially with a), difference is in embodiment 56: polymerization temperature is 10 DEG C.Co-catalyst dosage is the MAO of 3.1ml The toluene solution of (1.46mol/L), makes Al/Co=1500:1.Ethylene atmospheric pressure is 1atm.Polymerization activity: 1.17 × 10⁶g/ mol(Co)h^-1。

Substantially with a), difference is in embodiment 56: polymerization temperature is 20 DEG C.Co-catalyst dosage is the MAO of 3.1ml The toluene solution of (1.46mol/L), makes Al/Co=1500:1.Ethylene atmospheric pressure is 1atm.Polymerization activity: 1.41 × 10⁶g/ mol(Co)h^-1。

Substantially with a), difference is in embodiment 56: polymerization temperature is 30 DEG C.Co-catalyst dosage is the MAO of 3.1ml The toluene solution of (1.46mol/L), makes Al/Co=1500:1.Ethylene atmospheric pressure is 1atm.Polymerization activity: 1.61 × 10⁶g/ mol(Co)h^-1。

Substantially with a), difference is in embodiment 56: polymerization temperature is 40 DEG C.Co-catalyst dosage is the MAO of 3.1ml The toluene solution of (1.46mol/L), makes Al/Co=1500:1.Ethylene atmospheric pressure is 1atm.Polymerization activity: 1.66 × 10⁶g/ mol(Co)h^-1。

Substantially with a), difference is in embodiment 56: polymerization temperature is 50 DEG C.Co-catalyst dosage is the MAO of 3.1ml The toluene solution of (1.46mol/L), makes Al/Co=1500:1.Ethylene atmospheric pressure is 1atm.Polymerization activity: 1.22 × 10⁶g/ mol(Co)h^-1。

Substantially with a), difference is in embodiment 56: polymerization temperature is 60 DEG C.Co-catalyst dosage is the MAO of 3.1ml The toluene solution of (1.46mol/L), makes Al/Co=1500:1.Ethylene atmospheric pressure is 1atm.Polymerization activity: 0.75 × 10⁶g/ mol(Co)h^-1。

Substantially with a), difference is in embodiment 56: co-catalyst dosage is the toluene of the MAO (1.46mol/L) of 2.1ml Solution makes Al/Co=1000:1.Polymerization temperature is 40 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization activity: 1.35 × 10⁶g/mol (Co)h^-1。

Substantially with a), difference is in embodiment 56: co-catalyst dosage is the toluene of the MAO (1.46mol/L) of 4.1ml Solution makes Al/Co=2000:1.Polymerization temperature is 40 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization activity: 1.71 × 10⁶g/mol (Co)h^-1。

Substantially with a), difference is in embodiment 56: co-catalyst dosage is the toluene of the MAO (1.46mol/L) of 5.1ml Solution makes Al/Co=2500:1.Polymerization temperature is 40 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization activity: 1.47 × 10⁶g/mol (Co)h^-1。

Substantially with a), difference is in embodiment 56: co-catalyst dosage is the toluene of the MAO (1.46mol/L) of 6.2ml Solution makes Al/Co=3000:1.Polymerization temperature is 40 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization activity: 1.43 × 10⁶g/mol (Co)h^-1。

Substantially with a), difference is in embodiment 56: co-catalyst dosage is the toluene of the MAO (1.46mol/L) of 4.1ml Solution makes Al/Co=2000:1.Polymerization temperature is 40 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization time is 15min.Polymerization is lived Property: 2.01 × 10⁶g/mol(Co)h^-1。

Substantially with a), difference is in embodiment 56: co-catalyst dosage is the toluene of the MAO (1.46mol/L) of 4.1ml Solution makes Al/Co=2000:1.Polymerization temperature is 40 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization time is 45min.Polymerization is lived Property: 1.25 × 10⁶g/mol(Co)h^-1。

Substantially with a), difference is in embodiment 56: co-catalyst dosage is the toluene of the MAO (1.46mol/L) of 4.1ml Solution makes Al/Co=2000:1.Polymerization temperature is 40 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization time is 60min.Polymerization is lived Property: 1.01 × 10⁶g/mol(Co)h^-1。

Embodiment 75 combines the vinyl polymerization being catalyzed under normal pressure using complex Co-1 and MAO

Substantially with a), difference is: major catalyst Co-1 in embodiment 56；Co-catalyst dosage is the MAO of 4.1ml The toluene solution of (1.46mol/L), makes Al/Co=2000:1.Polymerization temperature is 40 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization is lived Property: 1.71 × 10⁶g/mol(Co)h^-1。

Embodiment 76 combines the vinyl polymerization being catalyzed under normal pressure using complex Co-2 and MAO

Substantially with a), difference is: major catalyst Co-2 in embodiment 56；Co-catalyst dosage is the MAO of 4.1ml The toluene solution of (1.46mol/L), makes Al/Co=2000:1.Polymerization temperature is 40 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization is lived Property: 1.67 × 10⁶g/mol(Co)h^-1。

Embodiment 77 combines the vinyl polymerization being catalyzed under normal pressure using complex Co-3 and MAO

Substantially with a), difference is: major catalyst Co-3 in embodiment 56；Co-catalyst dosage is the MAO of 4.1ml The toluene solution of (1.46mol/L), makes Al/Co=2000:1.Polymerization temperature is 40 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization is lived Property: 0.94 × 10⁶g/mol(Co)h^-1。

Embodiment 78 combines the vinyl polymerization being catalyzed under normal pressure using complex Co-5 and MAO

Substantially with a), difference is: major catalyst Co-5 in embodiment 56；Co-catalyst dosage is the MAO of 4.1ml The toluene solution of (1.46mol/L), makes Al/Co=2000:1.Polymerization temperature is 40 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization is lived Property: 1.61 × 10⁶g/mol(Co)h^-1。

Embodiment 79 combines the vinyl polymerization being catalyzed under normal pressure using complex Co-6 and MAO

Substantially with a), difference is: major catalyst Co-6 in embodiment 56；Co-catalyst dosage is the MAO of 4.1ml The toluene solution of (1.46mol/L), makes Al/Co=2000:1.Polymerization temperature is 40 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization is lived Property: 1.79 × 10⁶g/mol(Co)h^-1。

Embodiment 80 combines the vinyl polymerization being catalyzed under normal pressure using complex Co-7 and MAO

Substantially with a), difference is: major catalyst Co-7 in embodiment 56；Co-catalyst dosage is the MAO of 4.1ml The toluene solution of (1.46mol/L), makes Al/Co=2000:1.Polymerization temperature is 40 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization is lived Property: 1.70 × 10⁶g/mol(Co)h^-1。

Embodiment 77 combines the vinyl polymerization being catalyzed under normal pressure using complex Co-8 and MAO

Substantially with a), difference is: major catalyst Co-8 in embodiment 56；Co-catalyst dosage is the MAO of 4.1ml The toluene solution of (1.46mol/L), makes Al/Co=2000:1.Polymerization temperature is 40 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization is lived Property: 1.02 × 10⁶g/mol(Co)h^-1。

Embodiment 78 combines the vinyl polymerization being catalyzed under normal pressure using complex Co-9 and MAO

Substantially with a), difference is: major catalyst Co-9 in embodiment 56；Co-catalyst dosage is the MAO of 4.1ml The toluene solution of (1.46mol/L), makes Al/Co=2000:1.Polymerization temperature is 40 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization is lived Property: 1.48 × 10⁶g/mol(Co)h^-1。

Embodiment 79 combines the vinyl polymerization being catalyzed under normal pressure using complex Co-4 and MMAO

Substantially with a), difference is in embodiment 56: polymerization temperature is 10 DEG C.Co-catalyst dosage is the MMAO of 2.3ml The toluene solution of (2.0mol/L), makes Al/Co=1500:1.Ethylene atmospheric pressure is 1atm.Polymerization activity: 1.26 × 10⁶g/mol (Co)h^-1。

Substantially with a), difference is in embodiment 56: polymerization temperature is 20 DEG C.Co-catalyst dosage is the MMAO of 2.3ml The toluene solution of (2.0mol/L), makes Al/Co=1500:1.Ethylene atmospheric pressure is 1atm.Polymerization activity: 1.29 × 10⁶g/mol (Co)h^-1。

Substantially with a), difference is in embodiment 56: polymerization temperature is 30 DEG C.Co-catalyst dosage is the MMAO of 2.3ml The toluene solution of (2.0mol/L), makes Al/Co=1500:1.Ethylene atmospheric pressure is 1atm.Polymerization activity: 1.39 × 10⁶g/ mol(Co)h^-1。

Substantially with a), difference is in embodiment 56: polymerization temperature is 40 DEG C.Co-catalyst dosage is the MMAO of 2.3ml The toluene solution of (2.0mol/L), makes Al/Co=1500:1.Ethylene atmospheric pressure is 1atm.Polymerization activity: 1.15 × 10⁶g/mol (Co)h^-1。

Substantially with a), difference is in embodiment 56: polymerization temperature is 50 DEG C.Co-catalyst dosage is the MMAO of 2.3ml The toluene solution of (2.0mol/L), makes Al/Co=1500:1.Ethylene atmospheric pressure is 1atm.Polymerization activity: 1.00 × 10⁶g/mol (Co)h^-1。

Substantially with a), difference is in embodiment 56: polymerization temperature is 60 DEG C.Co-catalyst dosage is the MMAO of 2.3ml The toluene solution of (2.0mol/L), makes Al/Co=1500:1.Ethylene atmospheric pressure is 1atm.Polymerization activity: 0.48 × 10⁶g/mol (Co)h^-1。

Substantially with a), difference is in embodiment 56: co-catalyst dosage is the toluene of the MMAO (2.0mol/L) of 1.5ml Solution makes Al/Co=1000:1.Polymerization temperature is 30 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization activity: 1.33 × 10⁶g/mol (Co)h^-1。

Substantially with a), difference is in embodiment 56: co-catalyst dosage is the toluene of the MMAO (2.0mol/L) of 3.0ml Solution makes Al/Co=2000:1.Polymerization temperature is 30 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization activity: 1.45 × 10⁶g/mol (Co)h^-1。

Substantially with a), difference is in embodiment 56: co-catalyst dosage is the toluene of the MMAO (2.0mol/L) of 3.8ml Solution makes Al/Co=2500:1.Polymerization temperature is 30 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization activity: 1.51 × 10⁶g/mol (Co)h^-1。

Substantially with a), difference is in embodiment 56: co-catalyst dosage is the toluene of the MMAO (2.0mol/L) of 4.5ml Solution makes Al/Co=3000:1.Polymerization temperature is 30 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization activity: 1.39 × 10⁶g/mol (Co)h^-1。

Substantially with a), difference is in embodiment 56: co-catalyst dosage is the toluene of the MMAO (2.0mol/L) of 5.3ml Solution makes Al/Co=3500:1.Polymerization temperature is 30 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization activity: 1.34 × 10⁶ g/mol (Co)h^-1。

Embodiment 80 combines the vinyl polymerization being catalyzed under normal pressure using complex Co-1 and MMAO

Substantially with a), difference is: major catalyst Co-1 in embodiment 56；Co-catalyst dosage is the MMAO of 3.8ml The toluene solution of (2.0mol/L), makes Al/Co=2500:1.Polymerization temperature is 30 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization is lived Property: 1.61 × 10⁶g/mol(Co)h^-1。

Embodiment 81 combines the vinyl polymerization being catalyzed under normal pressure using complex Co-2 and MMAO

Substantially with a), difference is: major catalyst Co-2 in embodiment 56；Co-catalyst dosage is the MMAO of 3.8ml The toluene solution of (2.0mol/L), makes Al/Co=2500:1.Polymerization temperature is 30 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization is lived Property: 1.47 × 10⁶g/mol(Co)h^-1。

Embodiment 82 combines the vinyl polymerization being catalyzed under normal pressure using complex Co-3 and MMAO

Substantially with a), difference is: major catalyst Co-3 in embodiment 56；Co-catalyst dosage is the MMAO of 3.8ml The toluene solution of (2.0mol/L), makes Al/Co=2500:1.Polymerization temperature is 30 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization is lived Property: 1.06 × 10⁶g/mol(Co)h^-1。

Embodiment 83 combines the vinyl polymerization being catalyzed under normal pressure using complex Co-5 and MMAO

Substantially with a), difference is: major catalyst Co-5 in embodiment 56；Co-catalyst dosage is the MMAO of 3.8ml The toluene solution of (2.0mol/L), makes Al/Co=2500:1.Polymerization temperature is 30 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization is lived Property: 1.46 × 10⁶g/mol(Co)h^-1。

Embodiment 84 combines the vinyl polymerization being catalyzed under normal pressure using complex Co-6 and MMAO

Substantially with a), difference is: major catalyst Co-6 in embodiment 56；Co-catalyst dosage is the MMAO of 3.8ml The toluene solution of (2.0mol/L), makes Al/Co=2500:1.Polymerization temperature is 30 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization is lived Property: 1.65 × 10⁶g/mol(Co)h^-1。

Embodiment 85 combines the vinyl polymerization being catalyzed under normal pressure using complex Co-7 and MMAO

Substantially with a), difference is: major catalyst Co-7 in embodiment 56；Co-catalyst dosage is the MMAO of 3.8ml The toluene solution of (2.0mol/L), makes Al/Co=2500:1.Polymerization temperature is 30 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization is lived Property: 1.53 × 10⁶g/mol(Co)h^-1。

Embodiment 86 combines the vinyl polymerization being catalyzed under normal pressure using complex Co-8 and MMAO

Substantially with a), difference is: major catalyst Co-8 in embodiment 56；Co-catalyst dosage is the MMAO of 3.8ml The toluene solution of (2.0mol/L), makes Al/Co=2500:1.Polymerization temperature is 30 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization is lived Property: 1.16 × 10⁶g/mol(Co)h^-1。

Embodiment 87 combines the vinyl polymerization being catalyzed under normal pressure using complex Co-9 and MMAO

Substantially with a), difference is: major catalyst Co-9 in embodiment 56；Co-catalyst dosage is the MMAO of 3.8ml The toluene solution of (2.0mol/L), makes Al/Co=2500:1.Polymerization temperature is 30 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization is lived Property: 1.10 × 10⁶g/mol(Co)h^-1。

Reference examples 1, vinyl polymerization

50ml has been dissolved into the toluene solution of complex Fe-3 (3.0 μm of ol) and 50ml toluene is added sequentially to 250ml Stainless steel autoclave in, make total volume 100ml.When temperature reaches requirement polymerization temperature (10 DEG C), filled into reaction kettle Enter ethylene, keeps the ethylene pressure of 1MPa, be stirred to react 30min.It releases stress after reaction, reaction system is inactive.

Reference examples 2, vinyl polymerization

50ml has been dissolved into the toluene solution of complex Co-4 (3.0 μm of ol) and 50ml toluene is added sequentially to 250ml Stainless steel autoclave in, make total volume 100ml.When temperature reaches requirement polymerization temperature (30 DEG C), filled into reaction kettle Enter ethylene, keeps the ethylene pressure of 1MPa, be stirred to react 30min.It releases stress after reaction, reaction system is inactive.

Reference examples 3, vinyl polymerization

50ml toluene, methylaluminoxane (MAO) (4.1ml) and other 50ml toluene are added sequentially to 250ml not It becomes rusty in steel autoclave, makes total volume 100ml.When temperature reaches requirement polymerization temperature (10 DEG C), second is filled with into reaction kettle Alkene keeps the ethylene pressure of 1MPa, is stirred to react 30min.It releases stress after reaction, reaction system is inactive.

Reference examples 4, vinyl polymerization

50ml toluene, the methylaluminoxane (MMAO) (3.0ml) of modification and other 50ml toluene are added sequentially to In the stainless steel autoclave of 250ml, make total volume 100ml.When temperature reaches requirement polymerization temperature (10 DEG C), toward reaction kettle In be filled with ethylene, keep the ethylene pressure of 1MPa, be stirred to react 30min.It releases stress after reaction, reaction system is without work Property.

By above-mentioned reference examples 1-4 it is found that carbon monoxide-olefin polymeric of the invention shows good vinyl polymerization catalytic activity.

Claims

1. generation -2,9- the bis-imine pyridine of benzene shown in Formulas I and cycloheptane iron and cobalt complex:

Wherein, Ar¹、Ar²、Ar³It is independently from each other

Each R¹、R²、R³、R⁴、R⁵It is independently from each other H or C_1-6Alkyl-；

M is selected from Fe or Co；

X¹、X²Selected from Cl.

2. complex described in claim 1, in which:

R¹、R²、R³、R⁴、R⁵It is independently from each other H or methyl, ethyl, isopropyl.

3. complex of any of claims 1 or 2 has following group definition:

Fe-1:Ar³=Ph；Ar¹And Ar²In: R¹=Me, R²=H, R³=H, R⁴=H, R⁵=Me, M=Fe, X¹=X²=Cl；

Fe-2:Ar³=Ph；Ar¹And Ar²In: R¹=Et, R²=H, R³=H, R⁴=H, R⁵=Et, M=Fe, X¹=X²=Cl；

Fe-3:Ar³=Ph；Ar¹And Ar²In: R¹=i-Pr, R²=H, R³=H, R⁴=H, R⁵=i-Pr, M=Fe, X¹=X²=Cl；

Fe-4:Ar³=Ph；Ar¹And Ar²In: R¹=Me, R²=H, R³=Me, R⁴=H, R⁵=Me, M=Fe, X¹=X²=Cl；

Fe-5:Ar³=Ph；Ar¹And Ar²In: R¹=Et, R²=H, R³=Me, R⁴=H, R⁵=Et, M=Fe, X¹=X²=Cl；

Co-4:Ar³=Ph；Ar¹And Ar²In: R¹=Me, R²=H, R³=Me, R⁴=H, R⁵=Me, M=Co, X¹=X²=Cl.

4. the preparation method of any one of the claim 1-3 complex, including by compound shown in Formula IV, VII and FeCl₂· 4H₂O or CoCl₂Reaction, obtains complex shown in Formulas I:

Wherein, R¹、R²、R³、R⁴、R⁵、Ar¹、Ar²And Ar³With the group definition in claim any one of 1-3.

5. preparation method as claimed in claim 4, in which:

Compound and FeCl shown in Formula VII₂·4H₂O or CoCl₂Molar ratio be 1.00~1.05:0.90~1.00；

The reaction is carried out in the presence of acetic acid；

The reaction is back flow reaction；

Reaction time is 4-8 hours；

The reaction carries out under inert gas protection.

6. preparation method described in claim 5, in which:

Compound and FeCl shown in Formula VII₂·4H₂O or CoCl₂Molar ratio be 1.00:0.90；

The reaction uses acetic acid as solvent；

The reaction temperature is 140 DEG C；

Reaction time is 6 hours；

The inert gas is selected from nitrogen, argon gas or its gaseous mixture.

7. compound shown in Formula VII:

Wherein, Ar³With the definition in claim any one of 1-3.

8. the preparation method of compound described in claim 7, includes the following steps:

1) in the presence of Raney nickel, Formula II compound is reacted with cyanylation agent, obtains formula III compound；

Wherein Ar³With the definition in claim any one of 1-3, X is selected from Cl or Br.

9. preparation method according to any one of claims 8, in which:

The cyanylation agent of step 1) is potassium ferrocyanide, and the Raney nickel is bis- (diphenylphosphine) the propane chlorinations of 1,3- Nickel；

The reaction of step 2) carries out under conditions of p-methyl benzenesulfonic acid is as catalyst；

The reaction of step 4) carries out under conditions of p-methyl benzenesulfonic acid is as catalyst.

10. a kind of carbon monoxide-olefin polymeric for olefinic polymerization, including the described in any item complexs of claim 1-3, and Optional co-catalyst, wherein the co-catalyst is selected from methylaluminoxane (MAO) and modified methylaluminoxane (MMAO) One or two.

11. carbon monoxide-olefin polymeric described in any one of claim 10, wherein the alkene is ethylene.

12. a kind of method for preparing polyolefin, including making alkene in the presence of the carbon monoxide-olefin polymeric of claim 10 or 11 Carry out catalytic polymerization.

13. preparation method described in claim 12, wherein the alkene is ethylene.

14. the described in any item complexs of claim 1-3 are preparing the application in olefin polymerization catalysis.

15. application described in claim 14, wherein olefin polymerization catalysis is ethylene rolymerization catalyst.