CN106432357A

CN106432357A - Phenyl-2,9-diimine pyridine-cycloheptane iron and cobalt complex catalyst and preparing method and application thereof

Info

Publication number: CN106432357A
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: 2017-02-22
Anticipated expiration: 2035-08-10
Also published as: CN106432357B

Abstract

The invention relates to a Phenyl-2,9-diimine pyridine-cycloheptane iron and cobalt complex catalyst and a preparing method and an application thereof. The metal complex is used for catalyzing vinyl polymerization reaction, and has a very high catalytic activity, wherein the catalytic activities of the iron and the cobalt reach 1.56*10<7> g.mol<-1>(Fe).h<-1> and 1.42*10<7> g.mol<-1>(Co).h<-1> respectively; in addition, the complex catalyst can still maintain a high and enduring activity at a high temperature, thus having a broad industrial application prospect.

Description

Benzene generation -2,9- bis-imine pyridine cycloheptane ferrum and cobalt complex catalyst and preparation method and application

Technical field

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

Background technology

Polyolefin, as one of important synthetic material, is widely used in daily life and industrial and agricultural production, and its good opportunity to develop and potential development prospect all show that this kind of material will still be developed with speed faster from now on.Polyolefin industry flourishes after the application of the 1950's Ziegler-Natta type catalyst development, the developing history of 60 years so far.From initial Ziegler-Natta catalyst, oneself develops into current high-efficient high performance catalyst, the eighties in last century and the nineties develop metallocene catalyst and late transition metal catalyst again in succession, define the general layout of current multiple catalysts joint development, polyolefin is also changed from versatile material to functionalization material.At present, industrialized polyethylene catalysts 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) the efficient ethylene oligomerization of the late transition metal complex type developing, and in the last few years and polymerization catalyst.

Nineteen ninety-five, Brookhart seminar report alpha-diimine nickel (palladium) coordination compound can efficiently catalyzed ethylene polymerization, and obtain high molecular and the polymer of the various degree of branching.This discovery changes people it has long been believed that late transition metal is only used for causing olefin(e) oligomerization and is difficult to high poly- idea, has led the upsurge (J.Am.Chem.Soc., 1995,117,6414) of late transition metal catalyst catalysis in olefine polymerization research；Subsequently, in 1998, Brookhart and Gibson seminar independently reports pyridine diimine iron, cobalt complex, under MAO activation, show high ethylene catalyst activity, from the new neck that this has caused late transition metal catalyzed ethylene polymerization field a new step (its structure be shown below ((a) J.Am.Chem.Soc., 1998,120,4049；(b)Chem.Commun.,1998,849):

Round the basic skeleton structure of pyridine diimine, our seminars transform to the part of such catalyst, and successful design simultaneously develops multiclass ethylene oligomerization and the catalyst (following formula Fe1-Fe3) of polymerization.Wherein there are three kinds of ferrum system coordination compound Fe1-Fe3 of identical co-ordinating backbone and be demonstrated by distinct catalysis characteristicses in the presence of promoter MAO：Fe1 does not have catalysis activity, and Fe2 has a higher ethylene oligomerization 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 laid a good foundation for our the purposive models designing and synthesizing high activated catalyst.

Inventor has subsequently designed and developed the catalyst system (M1, M2, M3 and M4) of several new tridentates coordination, achieves good result, they all show excellent performance.Wherein, 2- benzimidazole -6- amido pyridine iron and cobalt complex M1 being capable of highly active catalytic ethylene oligomerization and polymerizations (Chinese Patent Application No. 200610165446.5, December 20 2006 applying date).And 2- benzothiazole -6- amido pyridine iron and cobalt complex M2 can obtain oligomer and Tissuemat E (Chinese Patent Application No. 200810239477.x, December 11 2008 year applying date) with more highly active catalytic ethylene oligomerization.2- amido -1 of seminar's exploitation in particularly 2005, the coordination compound M3 of 10- phenanthroline ferrum and cobalt, there is high ethylene oligomerization activity (Chinese Patent Application No. 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.Simultaneously, the 2 of three tooth nitrogen coordinations of inventor's design synthesis, 8- diimine quinoline M4 (Organometallics, 2010,29,1168) it is used for catalyzed ethylene polymerization to react, also show high catalysis activity, and resulting polymers molecular weight is high, narrow molecular weight distribution, catalyst has property of coincideing well to industrial operation temperature, has application potential.

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

Late transition metal complex catalyst structure is easy to modify, and to regulate and control product (polymer and oligomer) structure and molecular weight with this.However, as catalyst system of new generation, still also having difficult point and the restraining factors of some basic research during Industrialization.In general, late transition metal catalyst easily inactivates at high temperature, increases because chain tra nsfer termination speed is as the rising of temperature, and the heat stability of coordination compound itself is poor, thus causing activity to raise with reaction temperature and reduce.This limits the industrially applied research of metal complex catalysts to a certain extent.How to obtain higher active ethylene rolymerization catalyst and high ethylene polymerization activity can be kept in high temperature to become the core content of research, be also can to advance industrialized key as early as possible.The iron series of the designed synthesis of the present invention, Co catalysts, still can keep very high ethylene polymerization activity at high temperature, have great commercial application potentiality.And illustrate that such composition catalyst has the value of propulsion research.

Content of the invention

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

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

Each R¹、R²、R³、R⁴、R⁵It is independently from each other H, F, Cl, Br, I or the following groups optionally being replaced by one or more R '：C_1-6Alkyl-, C_1-6Alkyl oxy-, C_3-10Cycloalkyl-, C_3-10Cycloalkyl oxy-, C_6-14Aryl-, C_6-14Aryloxy-；

Each R ' is independently selected from F, Cl, Br, I or optionally by one or more R " following groups that replace：C_1-6Alkyl-, C_1-6Alkyl oxy-, C_3-10Cycloalkyl-, 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_6-14Aryloxy-；

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 has and is defined as below：

R¹、R²、R³、R⁴、R⁵It is independently from each other H, F, Cl, Br, I or the following groups optionally being replaced by one or more R '：C_1-6Alkyl-, C_1-6Alkyl oxy-, C_6-14Aryl-, C_6-14Aryloxy-；

Each R ' is independently selected from F, Cl, Br, I or optionally by one or more R " following groups that replace：Methyl, ethyl, propyl group, isopropyl, methoxyl group, ethyoxyl, phenyl, phenoxy group；

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

As example, R¹、R²、R³、R⁴、R⁵Be independently from each other H, F, Cl, Br, I or optionally by one or more R " methyl that replaces, ethyl, propyl group, isopropyl, methoxyl group, ethyoxyl, C_6-14Aryl C_1-6Alkyl-, two C_6-14Aryl C_1-6Alkyl-, such as phenyl methyl, phenylethyl, diphenyl methyl, diphenyl-ethyl, naphthyl methyl, naphtylethyl group, dinaphthyl ylmethyl, dinaphthyl ethyl；

Term " C_1-6Alkyl " is interpreted as preferably representing there is 1, 2, 3, 4, the linear or branched saturation monovalent hydrocarbon of 5 or 6 carbon atoms, such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, isopropyl, isobutyl group, sec-butyl, the tert-butyl group, isopentyl, 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- dimethylbutyl, 2, 2- dimethylbutyl, 1, 1- dimethylbutyl, 2, 3- dimethylbutyl, 1, 3- dimethylbutyl or 1, 2- dimethylbutyl or their isomer.Especially, described group has 1,2,3 or 4 carbon atom (" C_1-4Alkyl "), such as methyl, ethyl, propyl group, butyl, isopropyl, isobutyl group, sec-butyl, the tert-butyl group, more particularly, described group has 1,2 or 3 carbon atom (" C_1-3Alkyl "), such as methyl, ethyl, n-pro-pyl or isopropyl.

Term " C_3-10Cycloalkyl " is understood to mean that the monovalent monocyclic of saturation or bicyclic hydrocarbon ring, and it has 3,4,5,6,7,8,9 or 10 carbon atoms.Described C_3-10Cycloalkyl can be monocyclic alkyl, such as cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl, cyclononyl or cyclodecyl, or for example decahydronaphthalene naphthalene nucleus of bicyclic alkyl.

Term " C_6-14Aryl " is interpreted as preferably representing monocyclic, bicyclic or tricyclic the hydrocarbon ring (" C of the monovalence armaticity with 6,7,8,9,10,11,12,13 or 14 carbon atoms or partial aromatic_6-14Aryl "), particularly there is the ring (" C of 6 carbon atoms₆Aryl "), such as phenyl；Or xenyl, or there is the ring (" C of 9 carbon atoms₉Aryl "), such as indanyl or indenyl, or there is the ring (" C of 10 carbon atoms₁₀Aryl "), such as tetrahydro naphthyl, ihydro naphthyl or naphthyl, or there is the ring (" C of 13 carbon atoms₁₃Aryl "), such as fluorenyl, or there is the ring (" C of 14 carbon atoms₁₄Aryl "), such as anthryl.

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

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, and Ph represents phenyl, Ph₂CH represents benzhydryl.

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

Wherein, R¹、R²、R³、R⁴、R⁵And Ar³There is the group definition in above-mentioned Formulas I.

Actual conditions and parameter for above-mentioned reaction are not particularly limited, and those skilled in the art can select specific reaction condition and parameter as the case may be, to prepare target compound.Describe to following exemplary the available condition of this reaction and parameter, wherein one or more conditions and parameter can be applied to this reaction by those skilled in the art, or it is also possible to further modification or adjustment are carried out to them.

Compound shown in Formula VII and FeCl₂·4H₂O or CoCl₂Molar ratio be 1.00～1.05:0.90～1.00, such as 1.00:0.90；

Preferably, described reaction is carried out in the presence of acetic acid, acetic acid is more preferably used as solvent；Preferably, described react for back flow reaction, reaction temperature can be 140 DEG C；Preferably, the response time is 4-8 hour, such as 6 hours.

Preferably, described reaction is carried out under noble gases (such as nitrogen, argon or its gaseous mixture) protection.

According to the present invention, said method can also comprise the steps：By compound and FeCl shown in Formula IV, VII₂·4H₂O or CoCl₂The solution reacting the coordination compound shown in Formulas I obtaining concentrates, and adds poor solvent (such as ether) to precipitate, and precipitate is collected by filtration, and described precipitate is washed with poor solvent (such as ether), obtain final product target Formulas I coordination compound.

Present invention also offers compound shown in a kind of Formula VII：

Wherein, Ar³There is definition mentioned above.

The present invention also provides the preparation method of Formula VII compound, comprises the steps：

1) Formula II compound and cyanylation agent (such as potassium ferrocyanide) are reacted, and obtain formula III compound；

2) formula III compound and ethylene glycol carry out ketone protection reaction, obtain formula IV compound；

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

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

Wherein Ar³There is definition mentioned above, X is selected from Cl or Br.

Step 1) in：

Cyanylation agent can be 0.20-0.30 with the molar ratio of compound shown in Formula II:1, such as 0.25:1；Reaction is preferably carried out in the presence of Raney nickel (double (diphenylphosphine) the propane Nickel dichloride. of such as 1,3-), and the addition of Raney nickel can be 2%～5% of compound mole shown in Formula II；Cyanalation reaction can be carried out in organic solvent；Described organic solvent can be selected from least one in DMF and N-Methyl pyrrolidone, preferably N-Methyl pyrrolidone；Cyanalation reaction can be carried out under reflux conditions, and the response time of described reaction can be 8-16 hour, specially 12 hours.

Step 2) in：

Compound shown in formula III can be 1 with the molar ratio of ethylene glycol：1.5～2.5, such as 1:2.0；Reaction is preferably carried out under conditions of p-methyl benzenesulfonic acid is as catalyst, and the addition of p-methyl benzenesulfonic acid can be the 10%-20% of compound quality shown in formula III；Reaction can be carried out in organic solvent；Described organic solvent is selected from least one in toluene, dimethylbenzene and Isosorbide-5-Nitrae-dioxane, preferably toluene；Reaction can be carried out under reflux conditions, and the response time of described reaction is 8-16 hour, such as 12 hours.

Step 3) in：

Compound shown in formula IV can be 1 with the molar ratio of Grignard reagent：1.5-2.5, such as 1:2.0；Reaction is preferably carried out under the protection of noble gases (such as nitrogen, argon or its mixed gas)；Reaction can be carried out in organic solvent；Described organic solvent can be selected from least one in oxolane and absolute ether, preferably oxolane；Reaction can be carried out under cryogenic, between reaction temperature can be -10 DEG C -0 DEG C, such as -5 DEG C；The response time of reaction can be 0.5 hour.

Step 4) in：

Reaction is preferably carried out under conditions of p-methyl benzenesulfonic acid is as catalyst, and the addition of p-methyl benzenesulfonic acid can be the 10%-20% of Formula V compound quality, and such as 15%；Reaction can be carried out in organic solvent, and described organic solvent can be selected from acetone, the mixed solvent of Isosorbide-5-Nitrae-one or more of dioxane and water, such as 1, the mixed solvent of the mixed solvent of 4- dioxane and water, acetone and water, the preferably mixed solvent of Isosorbide-5-Nitrae-dioxane and water.In mixed solvent, the volume ratio of organic solvent and water can be 1～2:1～2, such as 1:1；Reaction can be carried out under reflux conditions, and the response time can be 4-8 hour, such as 6 hours.

In the preparation method of above-mentioned Formula VII compound, one or more purification steps as follows can also be included：

A) purification step of formula III compound：

By step 1) the formula III compound of gained is dissolved in organic solvent (as dichloromethane etc.), and silicagel column carries out column chromatography, with ethyl acetate:Petroleum ether=1:4 or dichloromethane:Petroleum ether=1:2 carry out eluting for eluant, detect eluted fraction by thin layer chromatography, remove solvent, obtain the formula III compound of purification；

B) purification step of formula IV compound：

By step 2) the formula IV compound of gained is dissolved in organic solvent (as dichloromethane etc.), and silicagel column carries out column chromatography, with ethyl acetate:Petroleum ether=1:10 or dichloromethane:Petroleum ether=1:5 carry out eluting for eluant, detect eluted fraction by thin layer chromatography, remove solvent, obtain the formula IV compound of purification.

C) purification step of Formula VII compound：

By step 4) the Formula VII compound of gained is dissolved in organic solvent (as dichloromethane etc.), and silicagel column carries out column chromatography, with ethyl acetate:Petroleum ether=1:10 or dichloromethane:Petroleum ether=1:5 carry out eluting for eluant, detect eluted fraction by thin layer chromatography, remove solvent, obtain the Formula VII compound of purification.

It is used for olefinic polymerization present invention also offers a kind of, the particularly carbon monoxide-olefin polymeric of vinyl polymerization, including the coordination compound of Formulas I, and optional promoter；

Described promoter can be included selected from one of MAO (MAO) and modified MAO (MMAO) or two kinds.

Described promoter can be 1000～3500 with the mol ratio of ferrum element in Formulas I coordination compound:1, preferably 2000～2500:1.

Described promoter can be 1000～3000 with the mol ratio of cobalt element in Formulas I coordination compound:1, preferably 1500～2500:1.

Present invention also offers one kind prepares polyolefin, the particularly method of polyethylene, carry out catalytic polymerization including in the presence of the carbon monoxide-olefin polymeric of the present invention, making alkene (as ethylene).

The exemplary condition of described polyreaction includes：

Promoter in iron complex carbon monoxide-olefin polymeric is MAO and described polyreaction is carried out at ambient pressure, and the polymerization temperature of described polyreaction is 0-30 DEG C, preferably 10 DEG C, and described normal pressure is 1atm.

Promoter in iron complex carbon monoxide-olefin polymeric is that MAO and described polyreaction are carried out under elevated pressure, and the polymerization temperature of described polyreaction is 40-80 DEG C, preferably 60 DEG C, described be pressurised into 1atm-10atm, but do not include 1atm.

Promoter in iron complex carbon monoxide-olefin polymeric is MMAO and described polyreaction is carried out at ambient pressure, and the polymerization temperature of described polyreaction is 0-40 DEG C, preferably 10 DEG C, and described normal pressure is 1atm.

Promoter in iron complex carbon monoxide-olefin polymeric is that MMAO and described polyreaction are carried out under elevated pressure, and the polymerization temperature of described polyreaction is 50-90 DEG C, preferably 70 DEG C, described be pressurised into 1atm-10atm, but do not include 1atm.

Promoter in cobalt complex catalyst compositionss is MAO and described polyreaction is carried out at ambient pressure, and the polymerization temperature of described polyreaction is 0-60 DEG C, preferably 40 DEG C；Described normal pressure is 1atm；

Promoter in cobalt complex catalyst compositionss is MAO and described polyreaction is carried out under elevated pressure, and the polymerization temperature of described polyreaction is 40-80 DEG C, preferably 60 DEG C；Described be pressurised into 1atm-10atm, but do not include 1atm；

Promoter in cobalt complex catalyst compositionss is MMAO and described polyreaction is carried out at ambient pressure, and the polymerization temperature of described polyreaction is 10-60 DEG C, preferably 30 DEG C；Described normal pressure is 1atm；

Promoter in cobalt complex catalyst compositionss is MMAO and described polyreaction is carried out under elevated pressure, and the polymerization temperature of described polyreaction is 50-90 DEG C, preferably 70 DEG C；Described be pressurised into 1atm-10atm, but do not include 1atm；

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

Polyreaction can be carried out in a solvent；Described solvent is selected from one of toluene and normal hexane or two kinds, preferably toluene.

Polyreaction can be carried out in inert atmosphere (such as nitrogen).

Present invention also offers Formulas I coordination compound is preparing olefin polymerization catalysis, the particularly application in ethylene rolymerization catalyst.

The present invention has designed and synthesized benzene generation -2, the 9- bis-imine pyridine containing N ' N ' N '-dentate cycloheptane ferrum and cobalt complex, and this metal complexes is used for catalyzed ethylene polymerization and reacts, shows very high catalysis activity, respectively reach 1.56 × 10⁷g·mol^-1(Fe)·h^-1And 1.42 × 10⁷g·mol^-1(Co)·h^-1, and such composition catalyst still can keep higher lasting activity at relatively high temperatures, has extensive prospects for commercial application.

Brief description

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

Below by specific embodiment, the present invention will be described, but the invention is not limited in this.

Experimental technique described in following embodiments, if no special instructions, is conventional method；Described reagent and material, if no special instructions, all commercially obtain.

Embodiment 1, preparation (E)-N- (((E) -9- (2,6- diisopropyl aniline) -6,7,8,9- tetrahydrochysene cycloheptane pyridine -2- benzyl enamine conjunction ferrous 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) under nitrogen protection, sequentially add 2- chloro- 5,6 in 150ml four-hole boiling flask; 7; 8- tetrahydrochysene cycloheptane pyridine -9- ketone (7.6g, 40mmol), potassium ferrocyanide (4.4g; 10mmol); 1,3- double (diphenylphosphine) propane Nickel dichloride .s (0.65g, 3mol%) and N-Methyl pyrrolidone 100ml; oil bath is warmed up to 150 DEG C of back flow reaction overnight, and raw material converts completely.Stop heating, silica gel post separation.Petroleum ether：Ethyl acetate=4:1 goes out target product, is yellow solid powder 4.2g, compound as shown in formula III, yield 56.5%.

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

3) under nitrogen protection, add compound (5.7g, 25mmol) and 100ml oxolane shown in formula IV in 250ml Jacketed bottle; logical -5 DEG C of ethanol bath; add phenyl-magnesium-bromide Grignard reagent (1M, 50ml) in system, stir half an hour after being added dropwise to complete.The water quenching of Deca 10ml is gone out reaction, stops stirring, stratification after half an hour.Separate water layer 50ml x 3 dichloromethane extraction after upper organic layer, merge organic layer and be concentrated to dryness.Obtain yellow oil 7.4g, compound as shown in Formula V, yield 95.8%.

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

5) under nitrogen protection; compound (0.132g shown in Formula VII; 0.5mmol), 2,6-DIPA (0.265g; 1.5mmol); Iron dichloride tetrahydrate (0.090g, 0.45mmol), 10ml glacial acetic acid is added to backflow 6h in 25ml round-bottomed flask; removal of solvent under reduced pressure simultaneously adds 50ml absolute ether, separates out a large amount of blue precipitate.It is dried to obtain blue powder 0.204g, compound Fe-3 as shown in Formulas I, yield 63.8%.

Structural identification data is as follows：

Formula III gained compound：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.

Formula IV gained compound：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.

Formula V gained compound：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.

Formula VII gained compound：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.

Step 5) gained coordination compound：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). elementary analysiss C₄₁H₄₉Cl₂FeN₃, theoretical value：C,69.30,H,6.95,N,5.91；Experiment value:C,69.12,H,6.89,N,6.96.

Data is confirmed from said structure, prepared compound is really target product Fe-3.

Embodiment 2, preparation (E)-N- (((E) -9- (2,6- dimethylaniline) -6,7,8,9- tetrahydrochysene cycloheptane pyridine -2- benzyl enamine conjunction ferrous 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 by the step 5 described in embodiment 1) in 2,6-DIPA be substituted for 2,6- dimethylaniline, obtain 0.235g blue powder, as belong to the Fe-1 of Formulas I, yield 87.3%.

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). elementary analysiss C₃₃H₃₃Cl₂FeN₃, theoretical value：C,66.24,H,5.56,N,7.02；Experiment value:C,66.26,H,5.54,N,6.84.

Data is confirmed from said structure, prepared compound is really target product Fe-1.

Embodiment 3, preparation (E)-N- (((E) -9- (2,6- diethylaniline) -6,7,8,9- tetrahydrochysene cycloheptane pyridine -2- benzyl enamine conjunction ferrous 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 by the step 5 described in embodiment 1) in 2,6-DIPA be substituted for 2,6- diethylaniline, obtain 0.203g blue powder, as belong to the Fe-2 of Formulas I, yield 69.0%.

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). elementary analysiss C₃₇H₄₁Cl₂FeN₃, theoretical value：C,67.90,H,6.31,N,6.42；Experiment value:C,67.50,H,6.25,N,6.32.

Data is confirmed from said structure, prepared compound is really target product Fe-2.

Embodiment 4, preparation (E)-N- (((E) -9- (2,4,6- trimethylaniline) -6,7,8,9- tetrahydrochysene cycloheptane pyridine -2- benzyl enamine conjunction ferrous 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 by the step 5 described in embodiment 1) in 2,6-DIPA be substituted for 2，4，6-trimethyl aniline, obtain 0.245g blue powder, as belong to the Fe-4 of Formulas I, yield 87.0%.

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). elementary analysiss C₃₅H₃₇Cl₂FeN₃, theoretical value：C,67.11,H,5.95,N,6.71；Experiment value:C,66.82,H,5.95,N,6.48.

Data is confirmed from said structure, prepared compound is really target product Fe-4.

Embodiment 5, preparation (E)-N- (((E) -9- (2,6- diethyl -4- monomethylaniline .) -6,7,8,9- tetrahydrochysene cycloheptane pyridine -2- benzyl enamine conjunction ferrous 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 the step 5 described in embodiment 1 is substituted for 2,6- diethyl -4- monomethylaniline., obtains 0.210g blue powder, as belong to the Fe-5 of Formulas I, yield 68.4%.

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). elementary analysiss C₃₉H₄₅Cl₂FeN₃, theoretical value：C,68.63,H,6.65,N,6.16；Experiment value:C,68.24,H,6.62,N,5.94.

Data is confirmed from said structure, prepared compound is really target product Fe-5.

Embodiment 6, preparation (E)-N- (((E) -9- (2,6- difluoro) -6,7,8,9- tetrahydrochysene cycloheptane pyridine -2- benzyl enamine conjunction ferrous 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 by the step 5 described in embodiment 1) in 2,6-DIPA be substituted for 2,6- difluoroaniline, obtain 0.225g blue powder, as belong to the Fe-6 of Formulas I, yield 73.3%.

Structural identification data is as follows:FT-IR(KBr,cm^-1):2920.3(m),2861.2(m),1601.3(ν_C ₌ _NM), 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). elementary analysiss C₂₉H₂₁Cl₂F₄FeN₃, theoretical value：C,56.71,H,3.45,N,6.84；Experiment value:C,56.26,H,3.54,N,6.84.

Data is confirmed from said structure, prepared compound is really target product Fe-6.

Embodiment 7, preparation (E)-N- (((E) -9- (2,6- dichloroaniline) -6,7,8,9- tetrahydrochysene cycloheptane pyridine -2- benzyl enamine conjunction ferrous 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 by the step 5 described in embodiment 1) in 2,6-DIPA be substituted for 2,6-DCA, obtain 0.303g blue powder, as belong to the Fe-7 of Formulas I, yield 89.1%.

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). elementary analysiss C₂₉H₂₁Cl₆FeN₃, theoretical value：C,51.22,H,3.11,N,6.18；Experiment value:C,52.00,H,3.09,N,6.12.

Data is confirmed from said structure, prepared compound is really target product Fe-7.

Embodiment 8, preparation (E)-N- (((E) -9- (2,6- dibromo aniline) -6,7,8,9- tetrahydrochysene cycloheptane pyridine -2- benzyl enamine conjunction ferrous 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 by the step 5 described in embodiment 1) in 2,6-DIPA be substituted for 2,6- dibromo aniline, obtain 0.345g blue powder, as belong to the Fe-8 of Formulas I, yield 80.4%.

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). elementary analysiss C₂₉H₂₁Br₄Cl₂FeN₃, theoretical value：C,40.60,H,2.47,N,4.90；Experiment value:C,40.32,H,2.43,N,4.79.

Data is confirmed from said structure, prepared compound is really target product Fe-8.

Embodiment 9, preparation (E)-N- (((E) -9- [2,6- bis- (benzhydryl) aniline] -6,7,8,9- tetrahydrochysene cycloheptane pyridine -2- benzyl enamine conjunction ferrous 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 by the step 5 described in embodiment 1) in 2,6-DIPA be substituted for 2,6- bis- (benzhydryl) aniline, obtain 0.410g blue powder, as belong to the Fe-9 of Formulas I, yield 67.9%.

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). elementary analysiss C₈₁H₆₅Cl₂FeN₃, theoretical value：C,80.59,H,5.43,N,3.48；Experiment value:C,80.24,H,5.45,N,3.41.

Data is confirmed from said structure, prepared compound is really target product Fe-9.

Embodiment 10, preparation (E)-N- (((E) -9- (2,6- dimethylaniline) -6,7,8,9- tetrahydrochysene cycloheptane pyridine -2- benzyl enamine conjunction cobaltous 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 by the step 5 described in embodiment 1) in 2,6-DIPA be substituted for 2,6- dimethylaniline, Iron dichloride tetrahydrate is substituted for cobaltous chloride, obtains 0.246g brownish-yellow powder, it is the Co-1 belonging to Formulas I, 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). elementary analysiss C₃₃H₃₃Cl₂CoN₃, theoretical value：C,65.90,H,5.53,N,6.99；Experiment value:C,65.63,H,5.60,N,6.96.

Data is confirmed from said structure, prepared coordination compound is really target product Co-1.

Embodiment 11, preparation (E)-N- (((E) -9- (2,6- diethylaniline) -6,7,8,9- tetrahydrochysene cycloheptane pyridine -2- benzyl enamine conjunction cobaltous 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 by the step 5 described in embodiment 1) in 2,6-DIPA be substituted for 2,6- diethylaniline, Iron dichloride tetrahydrate is substituted for cobaltous chloride, obtains 0.215g brownish-yellow powder, it is the Co-2 belonging to Formulas I, 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). elementary analysiss C₃₇H₄₁Cl₂CoN₃, theoretical value：C,67.58,H,6.28,N,6.39；Experiment value:C,67.29,H,6.10,N,6.29.

Data is confirmed from said structure, prepared coordination compound is really target product Co-2.

Embodiment 12, preparation (E)-N- (((E) -9- (2,6- diisopropyl aniline) -6,7,8,9- tetrahydrochysene cycloheptane pyridine -2- benzyl enamine conjunction cobaltous 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 by the step 5 described in embodiment 1) in Iron dichloride tetrahydrate be substituted for cobaltous chloride, obtain 0.180g brownish-yellow powder, as belong 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 near normal between pyridine ring and aniline as seen from the figure.

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). elementary analysiss C₄₁H₄₉Cl₂CoN₃, theoretical value：C,69.00,H,6.92,N,5.89；Experiment value:C,68.53,H,6.94,N,5.72.

Data is confirmed from said structure, prepared coordination compound is really target product Co-3.

Embodiment 13, preparation (E)-N- (((E) -9- (2,4,6- trimethylaniline) -6,7,8,9- tetrahydrochysene cycloheptane pyridine -2- benzyl enamine conjunction cobaltous 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 by the step 5 described in embodiment 1) in 2,6-DIPA be substituted for 2,4,6- trimethylanilines, Iron dichloride tetrahydrate is substituted for cobaltous chloride, obtain 0.213g brownish-yellow powder, as belong to the Co-4 of Formulas 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 ₌ _NM), 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). elementary analysiss C₃₅H₃₇Cl₂CoN₃, theoretical value：C,66.78,H,5.92,N,6.67；Experiment value:C,66.31,H,5.82,N,6.58.

Data is confirmed from said structure, prepared coordination compound is really target product Co-4.

Embodiment 14, preparation (E)-N- (((E) -9- (2,6- diethyl -4- monomethylaniline .) -6,7,8,9- tetrahydrochysene cycloheptane pyridine -2- benzyl enamine conjunction cobaltous 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 by the step 5 described in embodiment 1) in 2,6-DIPA be substituted for 2,6- diethyl -4- monomethylaniline., Iron dichloride tetrahydrate is substituted for cobaltous chloride, obtains 0.124g brownish-yellow powder, it is the Co-5 belonging to 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 ₌ _NM), 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). elementary analysiss C₃₉H₄₅Cl₂CoN₃, theoretical value：C,68.32,H,6.62,N,6.13；Experiment value:C,68.07,H,6.50,N,5.97.

Data is confirmed from said structure, prepared coordination compound is really target product Co-5.

Embodiment 15, preparation (E)-N- (((E) -9- (2,6- difluoro) -6,7,8,9- tetrahydrochysene cycloheptane pyridine -2- benzyl enamine conjunction cobaltous 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 by the step 5 described in embodiment 1) in 2,6-DIPA be substituted for 2,6- difluoroaniline, Iron dichloride tetrahydrate is substituted for cobaltous chloride, obtains 0.220g brown ceramic powder, it is the Co-6 belonging to Formulas I, yield 71.3%.

Structural identification data is as follows:FT-IR(KBr,cm^-1):2921.3(m),2861.5(m),1600.4(ν_C ₌ _NM), 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). elementary analysiss C₂₉H₂₁Cl₂F₄FeN₃, theoretical value：C,56.42,H,3.43,N,6.81；Experiment value:C,56.01,H,3.24,N,6.77.

Data is confirmed from said structure, prepared compound is really target product Co-6.

Embodiment 16, preparation (E)-N- (((E) -9- (2,6- dichloroaniline) -6,7,8,9- tetrahydrochysene cycloheptane pyridine -2- benzyl enamine conjunction cobaltous 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 by the step 5 described in embodiment 1) in 2,6-DIPA be substituted for 2,6- dichloroaniline, Iron dichloride tetrahydrate is substituted for cobaltous chloride, obtains 0.295g brown ceramic powder, it is the Co-7 belonging to Formulas I, 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). elementary analysiss C₂₉H₂₁Cl₆CoN₃, theoretical value：C,50.99,H,3.10,N,6.15；Experiment value:C,50.54,H,3.08,N,6.10.

Data is confirmed from said structure, prepared compound is really target product Co-7.

Embodiment 17, preparation (E)-N- (((E) -9- (2,6- dibromo aniline) -6,7,8,9- tetrahydrochysene cycloheptane pyridine -2- benzyl enamine conjunction cobaltous 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 by the step 5 described in embodiment 1) in 2,6-DIPA be substituted for 2,6- dibromo aniline, Iron dichloride tetrahydrate is substituted for cobaltous chloride, obtains 0.361g brown ceramic powder, it is the Co-8 belonging to Formulas I, 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). elementary analysiss C₂₉H₂₁Br₄Cl₂CoN₃, theoretical value：C,40.46,H,2.46,N,4.88；Experiment value:C,40.23,H,2.45,N,4.61.

Data is confirmed from said structure, prepared compound is really target product Co-8.

Embodiment 18, preparation (E)-N- (((E) -9- (2,6- bis- benzhydryl aniline) -6,7,8,9- tetrahydrochysene cycloheptane pyridine -2- benzyl enamine conjunction cobaltous 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 by the step 5 described in embodiment 1) in 2,6-DIPA be substituted for 2,6- bis- benzhydryl aniline, Iron dichloride tetrahydrate is substituted for cobaltous chloride, obtains 0.422g brown ceramic powder, it is the Co-9 belonging to Formulas 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). elementary analysiss C₈₁H₆₅Cl₂CoN₃, theoretical value：C,80.39,H,5.41,N,3.47；Experiment value:C,80.01,H,5.38,N,3.43.

Data is confirmed from said structure, prepared compound is really target product Co-9.

Embodiment 19, the vinyl polymerization combined using coordination compound Fe-3 and MAO under catalysis normal pressure：

A) under nitrogen protection, 50ml has been dissolved the toluene solution of coordination compound Fe-3 and the toluene solution of the promoter MAO (1.46mol/L) of 4.1ml and 50ml toluene has been added sequentially in 250ml reactor.Now, mechanical agitation starts, and keeps 400 revs/min, when temperature reaches 0 DEG C, is filled with ethylene toward in reactor, polyreaction starts.Keep the ethylene pressure of 1atm at 0 DEG C, stir 30min.With the ethanol solution neutralization reaction liquid of mass fraction 5% hydrochloric acid acidifying, obtain polymer precipitation, wash for several times with ethanol, vacuum drying is to constant weight.Polymerization activity：1.14×10⁶g/mol(Fe)h^-1.

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

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

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

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

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

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

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

Embodiment 20, the vinyl polymerization combined using coordination compound Fe-1 and MAO under catalysis normal pressure：

It is basic that with embodiment 19, a), difference is：Major catalyst is Fe-1；Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 5.1ml, makes Al/Fe=2500:1, polymerization temperature is 10 DEG C.Polymerization activity：2.59×10⁶g/mol(Fe)h^-1.

Embodiment 21, the vinyl polymerization combined using coordination compound Fe-2 and MAO under catalysis normal pressure：

It is basic that with embodiment 19, a), difference is：Major catalyst is Fe-2；Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 5.1ml, makes Al/Fe=2500:1, polymerization temperature is 10 DEG C.Polymerization activity：2.57×10⁶g/mol(Fe)h^-1.

Embodiment 22, the vinyl polymerization combined using coordination compound Fe-4 and MAO under catalysis normal pressure：

It is basic that with embodiment 19, a), difference is：Major catalyst is Fe-4；Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 5.1ml, makes Al/Fe=2500:1, polymerization temperature is 10 DEG C.Polymerization activity：2.26×10⁶g/mol(Fe)h^-1.

Embodiment 23, the vinyl polymerization combined using coordination compound Fe-5 and MAO under catalysis normal pressure：

It is basic that with embodiment 19, a), difference is：Major catalyst is Fe-5；Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 5.1ml, makes Al/Fe=2500:1, polymerization temperature is 10 DEG C.Polymerization activity：2.20×10⁶g/mol(Fe)h^-1.

Embodiment 24, the vinyl polymerization combined using coordination compound Fe-6 and MAO under catalysis normal pressure：

It is basic that with embodiment 19, a), difference is：Major catalyst is Fe-6；Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 5.1ml, makes Al/Fe=2500:1, polymerization temperature is 10 DEG C.Polymerization activity：2.90×10⁶g/mol(Fe)h^-1.

Embodiment 25, the vinyl polymerization combined using coordination compound Fe-7 and MAO under catalysis normal pressure：

It is basic that with embodiment 19, a), difference is：Major catalyst is Fe-7；Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 5.1ml, makes Al/Fe=2500:1, polymerization temperature is 10 DEG C.Polymerization activity：2.61×10⁶g/mol(Fe)h^-1.

Embodiment 27, the vinyl polymerization combined using coordination compound Fe-8 and MAO under catalysis normal pressure：

It is basic that with embodiment 19, a), difference is：Major catalyst is Fe-8；Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 5.1ml, makes Al/Fe=2500:1, polymerization temperature is 10 DEG C.Polymerization activity：2.01×10⁶g/mol(Fe)h^-1.

Embodiment 28, the vinyl polymerization combined using coordination compound Fe-9 and MAO under catalysis normal pressure：

It is basic that with embodiment 19, a), difference is：Major catalyst is Fe-9；Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 5.1ml, makes Al/Fe=2500:1, polymerization temperature is 10 DEG C.Polymerization activity：1.89×10⁶g/mol(Fe)h^-1.

Embodiment 29, the vinyl polymerization combined using coordination compound Fe-3 and MAO under catalysis pressurization：

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

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

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

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

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

It is basic that with embodiment 19, a), difference is：Polymerization temperature is 60 DEG C, and polymerization pressure is 10atm.Promoter consumption 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.

It is basic that with embodiment 19, a), difference is：Polymerization temperature is 60 DEG C, and polymerization pressure is 10atm.Promoter consumption 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.

It is basic that with embodiment 19, a), difference is：Polymerization temperature is 60 DEG C, and polymerization pressure is 10atm.Promoter consumption 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.

It is basic that with embodiment 19, a), difference is：Polymerization temperature is 60 DEG C, and polymerization pressure is 10atm.Promoter consumption 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.

It is basic that with embodiment 19, a), difference is：Polymerization temperature is 60 DEG C.Polymerization pressure is 5atm.Promoter consumption 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, the vinyl polymerization combined using coordination compound Fe-1 and MAO under catalysis high pressure：

It is basic that with embodiment 19, a), difference is：Major catalyst is Fe-1, and promoter consumption is the toluene solution of the MAO (1.46mol/L) of 5.1ml, makes Al/Fe=2500:1, polymerization temperature is 60 DEG C, and polymerization pressure is 10atm.Polymerization activity：15.09×10⁶g/mol(Fe)h^-1.

Embodiment 31, the vinyl polymerization combined using coordination compound Fe-2 and MAO under catalysis high pressure：

It is basic that with embodiment 19, a), difference is：Major catalyst is Fe-2；Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 5.1ml, makes Al/Fe=2500:1, polymerization temperature is 60 DEG C.Polymerization pressure is 10atm.Polymerization activity：10.65×10⁶g/mol(Fe)h^-1.

Embodiment 32, the vinyl polymerization combined using coordination compound Fe-4 and MAO under catalysis high pressure：

It is basic that with embodiment 19, a), difference is：Major catalyst is Fe-4, and promoter consumption is the toluene solution of the MAO (1.46mol/L) of 5.1ml, makes Al/Fe=2500:1, polymerization temperature is 60 DEG C, and polymerization pressure is 10atm.Polymerization activity：15.61×10⁶g/mol(Fe)h^-1.

Embodiment 33, the vinyl polymerization combined using coordination compound Fe-5 and MAO under catalysis high pressure：

It is basic that with embodiment 19, e), difference is：Major catalyst is Fe-5；Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 5.1ml, makes Al/Fe=2500:1, polymerization temperature is 60 DEG C, and polymerization pressure is 10atm.Polymerization activity：12.90×10⁶g/mol(Fe)h^-1.

Embodiment 34, the vinyl polymerization combined using coordination compound Fe-6 and MAO under catalysis high pressure：

It is basic that with embodiment 19, a), difference is：Major catalyst is Fe-6, and promoter consumption is the toluene solution of the MAO (1.46mol/L) of 5.1ml, makes Al/Fe=2500:1, polymerization temperature is 60 DEG C, and polymerization pressure is 10atm.Polymerization activity：15.22×10⁶g/mol(Fe)h^-1.

Embodiment 35, the vinyl polymerization combined using coordination compound Fe-7 and MAO under catalysis high pressure：

It is basic that with embodiment 19, a), difference is：Major catalyst is Fe-7；Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 5.1ml, makes Al/Fe=2500:1, polymerization temperature is 60 DEG C.Polymerization pressure is 10atm.Polymerization activity：10.95×10⁶g/mol(Fe)h^-1.

Embodiment 36, the vinyl polymerization combined using coordination compound Fe-8 and MAO under catalysis high pressure：

It is basic that with embodiment 19, a), difference is：Major catalyst is Fe-8, and promoter consumption is the toluene solution of the MAO (1.46mol/L) of 5.1ml, makes Al/Fe=2500:1, polymerization temperature is 60 DEG C, and polymerization pressure is 10atm.Polymerization activity：15.51×10⁶g/mol(Fe)h^-1.

Embodiment 37, the vinyl polymerization combined using coordination compound Fe-9 and MAO under catalysis high pressure：

It is basic that with embodiment 19, e), difference is：Major catalyst is Fe-9；Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 5.1ml, makes Al/Fe=2500:1, polymerization temperature is 60 DEG C, and polymerization pressure is 10atm.Polymerization activity：12.02×10⁶g/mol(Fe)h^-1.

Embodiment 38, the vinyl polymerization combined using coordination compound Fe-3 and MMAO under catalysis normal pressure：

It is basic that with embodiment 19, a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.0ml, makes Al/Fe=2000:1, polymerization temperature is 0 DEG C.Polymerization activity：1.26×10⁶g/mol(Fe)h^-1.

It is basic that with embodiment 19, a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.0ml, makes Al/Fe=2000:1, polymerization temperature is 10 DEG C.Polymerization activity：1.30×10⁶g/mol(Fe)h^-1.

It is basic that with embodiment 19, a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.0ml, makes Al/Fe=2000:1, polymerization temperature is 20 DEG C.Polymerization activity：1.25×10⁶g/mol(Fe)h^-1.

It is basic that with embodiment 19, a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.0ml, makes Al/Fe=2000:1, polymerization temperature is 30 DEG C.Polymerization activity：1.10×10⁶g/mol(Fe)h^-1.

It is basic that with embodiment 19, a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.0ml, makes Al/Fe=2000:1, polymerization temperature is 40 DEG C.Polymerization activity：0.71×10⁶g/mol(Fe)h^-1.

It is basic that with embodiment 19, a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 1.5ml, makes Al/Fe=1000:1, polymerization temperature is 10 DEG C.Polymerization activity：0.99×10⁶g/mol(Fe)h^-1.

It is basic that with embodiment 19, a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 2.3ml, makes Al/Fe=1500:1, polymerization temperature is 10 DEG C.Polymerization activity：1.23×10⁶g/mol(Fe)h^-1.

It is basic that with embodiment 19, a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.8ml, makes Al/Fe=2500:1, polymerization temperature is 10 DEG C.Polymerization activity：1.39×10⁶g/mol(Fe)h^-1.

It is basic that with embodiment 19, a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 4.5ml, makes Al/Fe=3000:1, polymerization temperature is 10 DEG C.Polymerization activity：1.33×10⁶g/mol(Fe)h^-1.

It is basic that with embodiment 19, a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 5.3ml, makes Al/Fe=3500:1, polymerization temperature is 10 DEG C.Polymerization activity：1.15×10⁶g/mol(Fe)h^-1.

It is basic that with embodiment 19, a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.8ml, makes Al/Fe=2500:1, polymerization temperature is 10 DEG C, and polymerization time is 15min.Polymerization activity：1.91×10⁶g/mol(Fe)h^-1.

It is basic that with embodiment 19, a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.8ml, makes Al/Fe=2500:1, polymerization temperature is 10 DEG C, and polymerization time is 45min.Polymerization activity：1.01×10⁶g/mol(Fe)h^-1.

It is basic that with embodiment 19, a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.8ml, makes Al/Fe=2500:1, polymerization temperature is 10 DEG C, and polymerization time is 60min.Polymerization activity：0.95×10⁶g/mol(Fe)h^-1.

Embodiment 39, the vinyl polymerization combined using coordination compound Fe-1 and MMAO under catalysis normal pressure：

It is basic that with embodiment 19, e), difference is：Major catalyst is Fe-1；Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.8ml, makes Al/Fe=2500:1, polymerization temperature is 10 DEG C.Polymerization activity：2.64×10⁶g/mol(Fe)h^-1.

Embodiment 40, the vinyl polymerization combined using coordination compound Fe-2 and MMAO under catalysis normal pressure：

It is basic that with embodiment 19, e), difference is：Major catalyst is Fe-2；Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.8ml, makes Al/Fe=2500:1, polymerization temperature is 10 DEG C.Polymerization activity：2.59×10⁶g/mol(Fe)h^-1.

Embodiment 41, the vinyl polymerization combined using coordination compound Fe-4 and MMAO under catalysis normal pressure：

It is basic that with embodiment 19, e), difference is：Major catalyst is Fe-4, and promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.8ml, makes Al/Fe=2500:1, polymerization temperature is 10 DEG C.Polymerization activity：2.53×10⁶g/mol(Fe)h^-1.

Embodiment 42, the vinyl polymerization combined using coordination compound Fe-5 and MMAO under catalysis normal pressure：

It is basic that with embodiment 19, e), difference is：Major catalyst is Fe-5, and promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.8ml, makes Al/Fe=2500:1, polymerization temperature is 10 DEG C.Polymerization activity：2.42×10⁶g/mol(Fe)h^-1.

Embodiment 43, the vinyl polymerization combined using coordination compound Fe-6 and MMAO under catalysis normal pressure：

It is basic that with embodiment 19, e), difference is：Major catalyst is Fe-6；Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.8ml, makes Al/Fe=2500:1, polymerization temperature is 10 DEG C.Polymerization activity：2.85×10⁶g/mol(Fe)h^-1.

Embodiment 44, the vinyl polymerization combined using coordination compound Fe-7 and MMAO under catalysis normal pressure：

It is basic that with embodiment 19, e), difference is：Major catalyst is Fe-7；Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.8ml, makes Al/Fe=2500:1, polymerization temperature is 10 DEG C.Polymerization activity：2.71×10⁶g/mol(Fe)h^-1.

Embodiment 45, the vinyl polymerization combined using coordination compound Fe-8 and MMAO under catalysis normal pressure：

It is basic that with embodiment 19, e), difference is：Major catalyst is Fe-8, and promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.8ml, makes Al/Fe=2500:1, polymerization temperature is 10 DEG C.Polymerization activity：2.63×10⁶g/mol(Fe)h^-1.

Embodiment 46, the vinyl polymerization combined using coordination compound Fe-9 and MMAO under catalysis normal pressure：

It is basic that with embodiment 19, e), difference is：Major catalyst is Fe-9, and promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.8ml, makes Al/Fe=2500:1, polymerization temperature is 10 DEG C.Polymerization activity：2.23×10⁶g/mol(Fe)h^-1.

Embodiment 47, the vinyl polymerization combined using coordination compound Fe-3 and MMAO under catalysis pressurization：

It is basic that with embodiment 19, a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.0ml, makes Al/Fe=2000:1, polymerization temperature is 50 DEG C, and polymerization pressure is 10atm.Polymerization activity：5.27×10⁶g/mol(Fe)h^-1.

It is basic that with embodiment 19, a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.0ml, makes Al/Fe=2000:1, polymerization temperature is 60 DEG C, and polymerization pressure is 10atm.Polymerization activity：7.04×10⁶g/mol(Fe)h^-1.

It is basic that with embodiment 19, a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.0ml, makes Al/Fe=2000:1, polymerization temperature is 70 DEG C, and polymerization pressure is 10atm.Polymerization activity：10.67×10⁶g/mol(Fe)h^-1.

It is basic that with embodiment 19, a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.0ml, makes Al/Fe=2000:1, polymerization temperature is 80 DEG C, and polymerization pressure is 10atm.Polymerization activity：4.83×10⁶g/mol(Fe)h^-1.

It is basic that with embodiment 19, a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.0ml, makes Al/Fe=2000:1, polymerization temperature is 90 DEG C, and polymerization pressure is 10atm.Polymerization activity：0.36×10⁶g/mol(Fe)h^-1.

It is basic that with embodiment 19, a), difference is：Polymerization temperature is 70 DEG C, and polymerization pressure is 10atm, and promoter consumption 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.

It is basic that with embodiment 19, a), difference is：Polymerization temperature is 70 DEG C, and polymerization pressure is 10atm, and promoter consumption 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.

It is basic that with embodiment 19, a), difference is：Polymerization temperature is 70 DEG C, and polymerization pressure is 10atm, and promoter consumption 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.

It is basic that with embodiment 19, a), difference is：Polymerization temperature is 70 DEG C.Polymerization pressure is 10atm, and promoter consumption 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.

It is basic that with embodiment 19, a), difference is：Polymerization temperature is 70 DEG C, and polymerization pressure is 5atm, and promoter consumption 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.

It is basic that with embodiment 19, a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.0ml, makes Al/Fe=2000:1, polymerization temperature is 70 DEG C, and polymerization time is 15min.Polymerization activity：15.52×10⁶g/mol(Fe)h^-1.

It is basic that with embodiment 19, a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.0ml, makes Al/Fe=2000:1, polymerization temperature is 70 DEG C, and polymerization time is 45min.Polymerization activity：8.37×10⁶g/mol(Fe)h^-1.

It is basic that with embodiment 19, a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.0ml, makes Al/Fe=2000:1, polymerization temperature is 70 DEG C, and polymerization time is 60min.Polymerization activity：6.66×10⁶g/mol(Fe)h^-1.

Embodiment 48, the vinyl polymerization combined using coordination compound Fe-1 and MMAO under catalysis high pressure：

It is basic that with embodiment 19, a), difference is：Major catalyst is Fe-1；Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.0ml, makes Al/Fe=2000:1, polymerization temperature is 70 DEG C, and polymerization pressure is 10atm.Polymerization activity：11.13×10⁶g/mol(Fe)h^-1.

Embodiment 49, the vinyl polymerization combined using coordination compound Fe-2 and MMAO under catalysis high pressure：

It is basic that with embodiment 19, a), difference is：Major catalyst is Fe-2；Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.0ml, makes Al/Fe=2000:1, polymerization temperature is 70 DEG C, and polymerization pressure is 10atm.Polymerization activity：8.77×10⁶g/mol(Fe)h^-1.

Embodiment 50, the vinyl polymerization combined using coordination compound Fe-4 and MMAO under catalysis high pressure：

It is basic that with embodiment 19, a), difference is：Major catalyst is Fe-4, and promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.0ml, makes Al/Fe=2000:1, polymerization temperature is 70 DEG C, and polymerization pressure is 10atm.Polymerization activity：13.36×10⁶g/mol(Fe)h^-1.

Embodiment 51, the vinyl polymerization combined using coordination compound Fe-5 and MMAO under catalysis high pressure：

It is basic that with embodiment 19, a), difference is：Major catalyst is Fe-5, and promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.0ml, makes Al/Fe=2000:1, polymerization temperature is 70 DEG C, and polymerization pressure is 10atm.Polymerization activity：9.17×10⁶g/mol(Fe)h^-1.

Embodiment 52, the vinyl polymerization combined using coordination compound Fe-6 and MMAO under catalysis high pressure：

It is basic that with embodiment 19, a), difference is：Major catalyst is Fe-6；Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.0ml, makes Al/Fe=2000:1, polymerization temperature is 70 DEG C, and polymerization pressure is 10atm.Polymerization activity：11.41×10⁶g/mol(Fe)h^-1.

Embodiment 53, the vinyl polymerization combined using coordination compound Fe-7 and MMAO under catalysis high pressure：

It is basic that with embodiment 19, a), difference is：Major catalyst is Fe-7；Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.0ml, makes Al/Fe=2000:1, polymerization temperature is 70 DEG C, and polymerization pressure is 10atm.Polymerization activity：8.90×10⁶g/mol(Fe)h^-1.

Embodiment 54, the vinyl polymerization combined using coordination compound Fe-8 and MMAO under catalysis high pressure：

It is basic that with embodiment 19, a), difference is：Major catalyst is Fe-8, and promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.0ml, makes Al/Fe=2000:1, polymerization temperature is 70 DEG C, and polymerization pressure is 10atm.Polymerization activity：13.50×10⁶g/mol(Fe)h^-1.

Embodiment 55, the vinyl polymerization combined using coordination compound Fe-9 and MMAO under catalysis high pressure：

It is basic that with embodiment 19, a), difference is：Major catalyst is Fe-9, and promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.0ml, makes Al/Fe=2000:1, polymerization temperature is 70 DEG C, and polymerization pressure is 10atm.Polymerization activity：8.97×10⁶g/mol(Fe)h^-1.

Embodiment 56, the vinyl polymerization combined using coordination compound Co-4 and MMAO under catalysis high pressure

A) under nitrogen protection, the toluene solution and 50ml toluene that have dissolved the promoter MMAO (2.0mol/L) of toluene solution 50ml and 2.3ml of catalyst Co-4 (3 μm of ol) are added sequentially in 250ml reactor.Now Al/Co=1500:1.Mechanical agitation starts, and keeps 400 revs/min, when polymerization temperature reaches 50 DEG C, is filled with ethylene toward in reactor, polyreaction starts.Keep the ethylene pressure of 10atm at 50 DEG C, stir 30min.With the ethanol solution neutralization reaction liquid of 5% hydrochloric acid acidifying, obtain polymer precipitation, wash for several times with ethanol, vacuum drying to constant weight, polymerization activity：1.95×10⁶g/mol(Co)h^-1.

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

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

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

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

Substantially same a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 1.5ml, Al/Co=1000:1, polymerization temperature is 70 DEG C.Polymerization activity：2.50×10⁶g/mol(Co)h^-1.

Substantially same a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.0ml, Al/Co=2000:1, polymerization temperature is 70 DEG C.Polymerization activity：2.92×10⁶g/mol(Co)h^-1.

Substantially same a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.8ml, Al/Co=2500:1, polymerization temperature is 70 DEG C.Polymerization activity：2.70×10⁶g/mol(Co)h^-1.

Substantially same a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 4.5ml, Al/Co=3000:1, polymerization temperature is 70 DEG C.Polymerization activity：2.18×10⁶g/mol(Co)h^-1.

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

Embodiment 57, the vinyl polymerization combined using coordination compound Co-1 and MMAO under catalysis high pressure

It is basic that with embodiment 56, a), difference is：Major catalyst is Co-1；Polymerization temperature is 70 DEG C.Polymerization activity：2.79×10⁶g/mol(Co)h^-1.

Embodiment 58, the vinyl polymerization combined using coordination compound Co-2 and MMAO under catalysis high pressure

It is basic that with embodiment 56, a), difference is：Major catalyst is Co-2；Polymerization temperature is 70 DEG C.Polymerization activity：2.67×10⁶g/mol(Co)h^-1.

Embodiment 59, the vinyl polymerization combined using coordination compound Co-3 and MMAO under catalysis high pressure

It is basic that with embodiment 56, a), difference is：Major catalyst is Co-3；Polymerization temperature is 70 DEG C.Polymerization activity：1.18×10⁶g/mol(Co)h^-1.

Embodiment 60, the vinyl polymerization combined using coordination compound Co-5 and MMAO under catalysis high pressure

It is basic that with embodiment 56, a), difference is：Major catalyst is Co-5；Polymerization temperature is 70 DEG C.Polymerization activity：2.95×10⁶g/mol(Co)h^-1.

Embodiment 61, the vinyl polymerization combined using coordination compound Co-6 and MMAO under catalysis high pressure

It is basic that with embodiment 56, a), difference is：Major catalyst is Co-6；Polymerization temperature is 70 DEG C.Polymerization activity：2.84×10⁶g/mol(Co)h^-1.

Embodiment 62, the vinyl polymerization combined using coordination compound Co-7 and MMAO under catalysis high pressure

It is basic that with embodiment 56, a), difference is：Major catalyst is Co-7；Polymerization temperature is 70 DEG C.Polymerization activity：2.71×10⁶g/mol(Co)h^-1.

Embodiment 63, the vinyl polymerization combined using coordination compound Co-8 and MMAO under catalysis high pressure

It is basic that with embodiment 56, a), difference is：Major catalyst is Co-8；Polymerization temperature is 70 DEG C.Polymerization activity：1.22×10⁶g/mol(Co)h^-1.

Embodiment 64, the vinyl polymerization combined using coordination compound Co-9 and MMAO under catalysis high pressure

It is basic that with embodiment 56, a), difference is：Major catalyst is Co-9；Polymerization temperature is 70 DEG C.Polymerization activity：2.85×10⁶g/mol(Co)h^-1.

Embodiment 65, the vinyl polymerization combined using coordination compound Co-4 and MAO under catalysis high pressure：

It is basic that with embodiment 56, a), difference is：Polymerization temperature is 40 DEG C.Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 3.1ml, makes Al/Co=1500:1.Polymerization activity：2.56×10⁶g/mol(Co)h^-1.

It is basic that with embodiment 56, a), difference is：Polymerization temperature is 50 DEG C.Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 3.1ml, makes Al/Co=1500:1.Polymerization activity：5.55×10⁶g/mol(Co)h^-1.

It is basic that with embodiment 56, a), difference is：Polymerization temperature is 60 DEG C.Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 3.1ml, makes Al/Co=1500:1.Polymerization activity：6.12×10⁶g/mol(Co)h^-1.

It is basic that with embodiment 56, a), difference is：Polymerization temperature is 70 DEG C.Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 3.1ml, makes Al/Co=1500:1.Polymerization activity：5.30×10⁶g/mol(Co)h^-1.

It is basic that with embodiment 56, a), difference is：Polymerization temperature is 80 DEG C.Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 3.1ml, makes Al/Co=1500:1.Polymerization activity：1.85×10⁶g/mol(Co)h^-1.

It is basic that with embodiment 56, a), difference is：Polymerization temperature is 90 DEG C.Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 3.1ml, makes Al/Co=1500:1.Polymerization activity：0.35×10⁶g/mol(Co)h^-1.

It is basic that with embodiment 56, a), difference is：Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 2.1ml, makes Al/Co=1000:1.Polymerization temperature is 60 DEG C.Polymerization activity：5.85×10⁶g/mol(Co)h^-1.

It is basic that with embodiment 56, a), difference is：Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 4.1ml, makes Al/Co=2000:1.Polymerization temperature is 60 DEG C.Polymerization activity：7.24×10⁶g/mol(Co)h^-1.

It is basic that with embodiment 56, a), difference is：Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 5.1ml, makes Al/Co=2500:1.Polymerization temperature is 60 DEG C.Polymerization activity：8.65×10⁶g/mol(Co)h^-1.

It is basic that with embodiment 56, a), difference is：Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 6.2ml, makes Al/Co=3000:1.Polymerization temperature is 60 DEG C.Polymerization activity：8.02×10⁶g/mol(Co)h^-1.

It is basic that with embodiment 56, a), difference is：Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 5.1ml, makes Al/Co=2500:1.Polymerization temperature is 60 DEG C.Response time is 10min.Polymerization activity：14.18×10⁶g/mol(Co)h^-1.

It is basic that with embodiment 56, a), difference is：Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 5.1ml, makes Al/Co=2500:1.Polymerization temperature is 60 DEG C.Response time is 20min.Polymerization activity：9.76×10⁶g/mol(Co)h^-1.

It is basic that with embodiment 56, a), difference is：Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 5.1ml, makes Al/Co=2500:1.Polymerization temperature is 60 DEG C.Response time is 45min.Polymerization activity：6.56×10⁶g/mol(Co)h^-1.

It is basic that with embodiment 56, a), difference is：Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 5.1ml, makes Al/Co=2500:1.Polymerization temperature is 60 DEG C.Response time is 60min.Polymerization activity：5.22×10⁶g/mol(Co)h^-1.

It is basic that with embodiment 56, a), difference is：Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 5.1ml, 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, the vinyl polymerization combined using coordination compound Co-1 and MAO under catalysis high pressure

It is basic that with embodiment 56, a), difference is：Major catalyst is Co-1；Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 5.1ml, makes Al/Co=2500:1.Polymerization temperature is 60 DEG C.Polymerization activity：8.15×10⁶g/mol(Co)h^-1.

Embodiment 67, the vinyl polymerization combined using coordination compound Co-2 and MAO under catalysis high pressure

It is basic that with embodiment 56, a), difference is：Major catalyst is Co-2；Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 5.1ml, makes Al/Co=2500:1.Polymerization temperature is 60 DEG C.Polymerization activity：6.19×10⁶g/mol(Co)h^-1.

Embodiment 68, the vinyl polymerization combined using coordination compound Co-3 and MAO under catalysis high pressure

It is basic that with embodiment 56, a), difference is：Major catalyst is Co-3；Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 5.1ml, makes Al/Co=2500:1.Polymerization temperature is 60 DEG C.Polymerization activity：5.66×10⁶g/mol(Co)h^-1.

Embodiment 69, the vinyl polymerization combined using coordination compound Co-5 and MAO under catalysis high pressure

It is basic that with embodiment 56, a), difference is：Major catalyst is Co-5；Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 5.1ml, makes Al/Co=2500:1.Polymerization temperature is 60 DEG C.Polymerization activity：6.38×10⁶g/mol(Co)h^-1.

Embodiment 70, the vinyl polymerization combined using coordination compound Co-6 and MAO under catalysis high pressure

It is basic that with embodiment 56, a), difference is：Major catalyst is Co-6；Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 5.1ml, makes Al/Co=2500:1.Polymerization temperature is 60 DEG C.Polymerization activity：8.23×10⁶g/mol(Co)h^-1.

Embodiment 71, the vinyl polymerization combined using coordination compound Co-7 and MAO under catalysis high pressure

It is basic that with embodiment 56, a), difference is：Major catalyst is Co-7；Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 5.1ml, makes Al/Co=2500:1.Polymerization temperature is 60 DEG C.Polymerization activity：6.25×10⁶g/mol(Co)h^-1.

Embodiment 72, the vinyl polymerization combined using coordination compound Co-8 and MAO under catalysis high pressure

It is basic that with embodiment 56, a), difference is：Major catalyst is Co-8；Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 5.1ml, makes Al/Co=2500:1.Polymerization temperature is 60 DEG C.Polymerization activity：5.80×10⁶g/mol(Co)h^-1.

Embodiment 73, the vinyl polymerization combined using coordination compound Co-9 and MAO under catalysis high pressure

It is basic that with embodiment 56, a), difference is：Major catalyst is Co-9；Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 5.1ml, makes Al/Co=2500:1.Polymerization temperature is 60 DEG C.Polymerization activity：6.01×10⁶g/mol(Co)h^-1.

Embodiment 74, the vinyl polymerization combined using coordination compound Co-4 and MAO under catalysis normal pressure

It is basic that with embodiment 56, a), difference is：Polymerization temperature is 0 DEG C.Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 3.1ml, makes Al/Co=1500:1.Ethylene atmospheric pressure is 1atm.Polymerization activity：0.86×10⁶g/mol(Co)h^-1.

It is basic that with embodiment 56, a), difference is：Polymerization temperature is 10 DEG C.Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 3.1ml, makes Al/Co=1500:1.Ethylene atmospheric pressure is 1atm.Polymerization activity：1.17×10⁶g/mol(Co)h^-1.

It is basic that with embodiment 56, a), difference is：Polymerization temperature is 20 DEG C.Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 3.1ml, makes Al/Co=1500:1.Ethylene atmospheric pressure is 1atm.Polymerization activity：1.41×10⁶g/mol(Co)h^-1.

It is basic that with embodiment 56, a), difference is：Polymerization temperature is 30 DEG C.Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 3.1ml, makes Al/Co=1500:1..Ethylene atmospheric pressure is 1atm.Polymerization activity：1.61×10⁶g/mol(Co)h^-1.

It is basic that with embodiment 56, a), difference is：Polymerization temperature is 40 DEG C.Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 3.1ml, makes Al/Co=1500:1.Ethylene atmospheric pressure is 1atm.Polymerization activity：1.66×10⁶g/mol(Co)h^-1.

It is basic that with embodiment 56, a), difference is：Polymerization temperature is 50 DEG C.Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 3.1ml, makes Al/Co=1500:1.Ethylene atmospheric pressure is 1atm.Polymerization activity：1.22×10⁶g/mol(Co)h^-1.

It is basic that with embodiment 56, a), difference is：Polymerization temperature is 60 DEG C.Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 3.1ml, makes Al/Co=1500:1.Ethylene atmospheric pressure is 1atm.Polymerization activity：0.75×10⁶g/mol(Co)h^-1.

It is basic that with embodiment 56, a), difference is：Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 2.1ml, 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.

It is basic that with embodiment 56, a), difference is：Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 4.1ml, 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.

It is basic that with embodiment 56, a), difference is：Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 5.1ml, 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.

It is basic that with embodiment 56, a), difference is：Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 6.2ml, 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.

It is basic that with embodiment 56, a), difference is：Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 4.1ml, makes Al/Co=2000:1.Polymerization temperature is 40 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization time is 15min.Polymerization activity：2.01×10⁶g/mol(Co)h^-1.

It is basic that with embodiment 56, a), difference is：Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 4.1ml, makes Al/Co=2000:1.Polymerization temperature is 40 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization time is 45min.Polymerization activity：1.25×10⁶g/mol(Co)h^-1.

It is basic that with embodiment 56, a), difference is：Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 4.1ml, makes Al/Co=2000:1.Polymerization temperature is 40 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization time is 60min.Polymerization activity：1.01×10⁶g/mol(Co)h^-1.

Embodiment 75, the vinyl polymerization combined using coordination compound Co-1 and MAO under catalysis normal pressure

It is basic that with embodiment 56, a), difference is：Major catalyst is Co-1；Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 4.1ml, 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.

Embodiment 76, the vinyl polymerization combined using coordination compound Co-2 and MAO under catalysis normal pressure

It is basic that with embodiment 56, a), difference is：Major catalyst is Co-2；Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 4.1ml, makes Al/Co=2000:1.Polymerization temperature is 40 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization activity：1.67×10⁶g/mol(Co)h^-1.

Embodiment 77, the vinyl polymerization combined using coordination compound Co-3 and MAO under catalysis normal pressure

It is basic that with embodiment 56, a), difference is：Major catalyst is Co-3；Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 4.1ml, makes Al/Co=2000:1.Polymerization temperature is 40 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization activity：0.94×10⁶g/mol(Co)h^-1.

Embodiment 78, the vinyl polymerization combined using coordination compound Co-5 and MAO under catalysis normal pressure

It is basic that with embodiment 56, a), difference is：Major catalyst is Co-5；Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 4.1ml, makes Al/Co=2000:1.Polymerization temperature is 40 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization activity：1.61×10⁶g/mol(Co)h^-1.

Embodiment 79, the vinyl polymerization combined using coordination compound Co-6 and MAO under catalysis normal pressure

It is basic that with embodiment 56, a), difference is：Major catalyst is Co-6；Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 4.1ml, makes Al/Co=2000:1.Polymerization temperature is 40 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization activity：1.79×10⁶g/mol(Co)h^-1.

Embodiment 80, the vinyl polymerization combined using coordination compound Co-7 and MAO under catalysis normal pressure

It is basic that with embodiment 56, a), difference is：Major catalyst is Co-7；Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 4.1ml, makes Al/Co=2000:1.Polymerization temperature is 40 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization activity：1.70×10⁶g/mol(Co)h^-1.

Embodiment 77, the vinyl polymerization combined using coordination compound Co-8 and MAO under catalysis normal pressure

It is basic that with embodiment 56, a), difference is：Major catalyst is Co-8；Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 4.1ml, makes Al/Co=2000:1.Polymerization temperature is 40 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization activity：1.02×10⁶g/mol(Co)h^-1.

Embodiment 78, the vinyl polymerization combined using coordination compound Co-9 and MAO under catalysis normal pressure

It is basic that with embodiment 56, a), difference is：Major catalyst is Co-9；Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 4.1ml, makes Al/Co=2000:1.Polymerization temperature is 40 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization activity：1.48×10⁶g/mol(Co)h^-1.

Embodiment 79, the vinyl polymerization combined using coordination compound Co-4 and MMAO under catalysis normal pressure

It is basic that with embodiment 56, a), difference is：Polymerization temperature is 10 DEG C.Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 2.3ml, makes Al/Co=1500:1.Ethylene atmospheric pressure is 1atm.Polymerization activity：1.26×10⁶g/mol(Co)h^-1.

It is basic that with embodiment 56, a), difference is：Polymerization temperature is 20 DEG C.Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 2.3ml, makes Al/Co=1500:1.Ethylene atmospheric pressure is 1atm.Polymerization activity：1.29×10⁶g/mol(Co)h^-1.

It is basic that with embodiment 56, a), difference is：Polymerization temperature is 30 DEG C.Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 2.3ml, makes Al/Co=1500:1..Ethylene atmospheric pressure is 1atm.Polymerization activity：1.39×10⁶g/mol(Co)h^-1.

It is basic that with embodiment 56, a), difference is：Polymerization temperature is 40 DEG C.Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 2.3ml, makes Al/Co=1500:1.Ethylene atmospheric pressure is 1atm.Polymerization activity：1.15×10⁶g/mol(Co)h^-1.

It is basic that with embodiment 56, a), difference is：Polymerization temperature is 50 DEG C.Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 2.3ml, makes Al/Co=1500:1.Ethylene atmospheric pressure is 1atm.Polymerization activity：1.00×10⁶g/mol(Co)h^-1.

It is basic that with embodiment 56, a), difference is：Polymerization temperature is 60 DEG C.Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 2.3ml, makes Al/Co=1500:1.Ethylene atmospheric pressure is 1atm.Polymerization activity：0.48×10⁶g/mol(Co)h^-1.

It is basic that with embodiment 56, a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 1.5ml, 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.

It is basic that with embodiment 56, a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.0ml, 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.

It is basic that with embodiment 56, a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.8ml, 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.

It is basic that with embodiment 56, a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 4.5ml, 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.

It is basic that with embodiment 56, a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 5.3ml, makes Al/Co=3500:1.Polymerization temperature is 30 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization activity：1.34×10⁶g/mol(Co)h^-1.

Embodiment 80, the vinyl polymerization combined using coordination compound Co-1 and MMAO under catalysis normal pressure

It is basic that with embodiment 56, a), difference is：Major catalyst is Co-1；Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.8ml, makes Al/Co=2500:1.Polymerization temperature is 30 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization activity：1.61×10⁶g/mol(Co)h^-1.

Embodiment 81, the vinyl polymerization combined using coordination compound Co-2 and MMAO under catalysis normal pressure

It is basic that with embodiment 56, a), difference is：Major catalyst is Co-2；Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.8ml, makes Al/Co=2500:1.Polymerization temperature is 30 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization activity：1.47×10⁶g/mol(Co)h^-1.

Embodiment 82, the vinyl polymerization combined using coordination compound Co-3 and MMAO under catalysis normal pressure

It is basic that with embodiment 56, a), difference is：Major catalyst is Co-3；Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.8ml, makes Al/Co=2500:1.Polymerization temperature is 30 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization activity：1.06×10⁶g/mol(Co)h^-1.

Embodiment 83, the vinyl polymerization combined using coordination compound Co-5 and MMAO under catalysis normal pressure

It is basic that with embodiment 56, a), difference is：Major catalyst is Co-5；Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.8ml, makes Al/Co=2500:1.Polymerization temperature is 30 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization activity：1.46×10⁶g/mol(Co)h^-1.

Embodiment 84, the vinyl polymerization combined using coordination compound Co-6 and MMAO under catalysis normal pressure

It is basic that with embodiment 56, a), difference is：Major catalyst is Co-6；Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.8ml, makes Al/Co=2500:1.Polymerization temperature is 30 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization activity：1.65×10⁶g/mol(Co)h^-1.

Embodiment 85, the vinyl polymerization combined using coordination compound Co-7 and MMAO under catalysis normal pressure

It is basic that with embodiment 56, a), difference is：Major catalyst is Co-7；Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.8ml, makes Al/Co=2500:1.Polymerization temperature is 30 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization activity：1.53×10⁶g/mol(Co)h^-1.

Embodiment 86, the vinyl polymerization combined using coordination compound Co-8 and MMAO under catalysis normal pressure

It is basic that with embodiment 56, a), difference is：Major catalyst is Co-8；Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.8ml, makes Al/Co=2500:1.Polymerization temperature is 30 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization activity：1.16×10⁶g/mol(Co)h^-1.

Embodiment 87, the vinyl polymerization combined using coordination compound Co-9 and MMAO under catalysis normal pressure

It is basic that with embodiment 56, a), difference is：Major catalyst is Co-9；Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.8ml, makes Al/Co=2500:1.Polymerization temperature is 30 DEG C.Ethylene atmospheric pressure is 1atm.Polymerization activity：1.10×10⁶g/mol(Co)h^-1.

Reference examples 1, vinyl polymerization

50ml is dissolved the toluene solution of coordination compound Fe-3 (3.0 μm of ol) and 50ml toluene has been added sequentially in the stainless steel autoclave of 250ml, made cumulative volume be 100ml.When temperature reaches requirement polymerization temperature (10 DEG C), it is filled with ethylene toward in reactor, keep the ethylene pressure of 1MPa, stirring reaction 30min.Reaction discharges pressure after terminating, and reaction system is inactive.

Reference examples 2, vinyl polymerization

50ml is dissolved the toluene solution of coordination compound Co-4 (3.0 μm of ol) and 50ml toluene has been added sequentially in the stainless steel autoclave of 250ml, made cumulative volume be 100ml.When temperature reaches requirement polymerization temperature (30 DEG C), it is filled with ethylene toward in reactor, keep the ethylene pressure of 1MPa, stirring reaction 30min.Reaction discharges pressure after terminating, and reaction system is inactive.

Reference examples 3, vinyl polymerization

50ml toluene, MAO (MAO) (4.1ml) and other 50ml toluene are added sequentially in the stainless steel autoclave of 250ml, make cumulative volume be 100ml.When temperature reaches requirement polymerization temperature (10 DEG C), it is filled with ethylene toward in reactor, keep the ethylene pressure of 1MPa, stirring reaction 30min.Reaction discharges pressure after terminating, and reaction system is inactive.

Reference examples 4, vinyl polymerization

50ml toluene, modified MAO (MMAO) (3.0ml) and other 50ml toluene are added sequentially in the stainless steel autoclave of 250ml, make cumulative volume be 100ml.When temperature reaches requirement polymerization temperature (10 DEG C), it is filled with ethylene toward in reactor, keep the ethylene pressure of 1MPa, stirring reaction 30min.Reaction discharges pressure after terminating, and reaction system is inactive.

From above-mentioned reference examples 1-4, the carbon monoxide-olefin polymeric of the present invention shows good vinyl polymerization catalysis activity.

Claims

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

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

Each R¹、R²、R³、R⁴、R⁵It is independently from each other H, F, Cl, Br, I or optionally by one or more R^’The following groups replacing：C_1-6Alkyl-, C_1-6Alkyl oxy-, C_3-10Cycloalkyl-, C_3-10Cycloalkyl oxy-, C_6-14Aryl-, C_6-14Aryloxy-；

M is selected from Fe or Co；

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

2. the coordination compound described in claim 1, wherein：

R¹、R²、R³、R⁴、R⁵It is independently from each other H, F, Cl, Br, I or optionally by one or more R^’The following groups replacing：C_1-6Alkyl-, C_1-6Alkyl oxy-, C_6-14Aryl-, C_6-14Aryloxy-；

3. the coordination compound described in claim 1 or 2, wherein：

R¹、R²、R³、R⁴、R⁵Be independently from each other H, F, Cl, Br, I or optionally by one or more R " methyl that replaces, ethyl, propyl group, isopropyl, methoxyl group, ethyoxyl, C_6-14Aryl C_1-6Alkyl-, two C_6-14Aryl C_1-6Alkyl-, such as phenyl methyl, phenylethyl, diphenyl methyl, diphenyl-ethyl, naphthyl methyl, naphtylethyl group, dinaphthyl ylmethyl, dinaphthyl ethyl；

4. the coordination compound described in any one of claim 1-3, has following group definition：

5. the preparation method of coordination compound described in any one of claim 1-4, including by compound and FeCl shown in Formula IV, VII₂·4H₂O or CoCl₂Reaction, obtains coordination compound shown in Formulas I：

Wherein, R¹、R²、R³、R⁴、R⁵、Ar¹、Ar²And Ar³There is the group definition in any one of claim 1-4；

Preferably,

Described reaction is carried out in the presence of acetic acid, acetic acid is more preferably used as solvent；

Described react for back flow reaction, reaction temperature can be 140 DEG C；

Response time is 4-8 hour, such as 6 hours.

Described reaction is carried out under noble gases (such as nitrogen, argon or its gaseous mixture) protection.

6. compound shown in Formula VII：

Wherein, Ar³There is the definition in any one of claim 1-4.

7. the preparation method of compound described in claim 6, comprises the steps：

Wherein Ar³There is the definition in any one of claim 1-4, X is selected from Cl or Br；

Preferably,

Step 1) reaction preferably carry out in the presence of Raney nickel (such as 1,3- double (diphenylphosphine) propane Nickel dichloride .)；

Step 2) reaction preferably carry out under conditions of p-methyl benzenesulfonic acid is as catalyst；

Step 4) reaction preferably carry out under conditions of p-methyl benzenesulfonic acid is as catalyst.

8. one kind is used for olefinic polymerization, the carbon monoxide-olefin polymeric of particularly vinyl polymerization, coordination compound including Formulas I, and optional promoter, wherein said promoter can include selected from one of MAO (MAO) and modified MAO (MMAO) or two kinds.

9. one kind prepares polyolefin, the particularly method of polyethylene, carries out catalytic polymerization including in the presence of the carbon monoxide-olefin polymeric of claim 8, making alkene (as ethylene).

10. the Formulas I coordination compound described in any one of claim 1-4 is preparing olefin polymerization catalysis, the particularly application in ethylene rolymerization catalyst.