CN106432356A - Alpha,alpha'-diarylimino-di(pentamethylene)pyridine complex, and preparation method and application thereof - Google Patents

Alpha,alpha'-diarylimino-di(pentamethylene)pyridine complex, and preparation method and application thereof Download PDF

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CN106432356A
CN106432356A CN201510487654.6A CN201510487654A CN106432356A CN 106432356 A CN106432356 A CN 106432356A CN 201510487654 A CN201510487654 A CN 201510487654A CN 106432356 A CN106432356 A CN 106432356A
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polymerization
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杜世振
张文娟
孙文华
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Institute of Chemistry CAS
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Institute of Chemistry CAS
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Abstract

The invention discloses an alpha,alpha'-diarylimino-2,3:5,6-di(pentamethylene)pyridine iron and cobalt complex catalyst, and a preparation method and an application thereof. The structural formula of the complex is represented by formula I; and R in the formula I is at least one selected from a methyl group, an ethyl group, an isopropyl group, fluorine, chlorine and bromine. The preparation method is characterized in that a refluxing reaction of a compound represented by formula II, a compound represented by formula III and FeCl2.4H2O or CoCl2 in acetic acid used as a solvent to obtain the complex represented by the formula I. The alpha,alpha'-diarylimino-2,3:5,6-di(pentamethylene)pyridine iron and cobalt complex can highly actively catalyze ethylene polymerization under the action of a cocatalyst methylaluminoxane and modified methylaluminoxane in order to obtain linear polyethylene. The complex has a good industrial application prospect.

Description

α, α '-bis-arylimine-two（Pentamethylene）Pyridines coordination compound and preparation method and its application
Technical field
The present invention relates to a class contains α, α '-bis-arylimine -2,3:5,6- and two (pentamethylene) pyridine iron, cobalt complex and preparation method thereof, and the application that such coordination compound is prepared in catalyzed ethylene polymerization.
Background technology
Polyethylene has the advantages that cost performance height, good mechanical properties, processing characteristics be excellent, hot property and stable chemical performance and be widely used in the every field of the national economy such as daily life, health care, industrial or agricultural and Aero-Space and the national defense and military of the mankind.And alkene catalyst be polyethylene field research crucial, the polyolefinic performance of its development and structures shape.Make a general survey of the development course of polyolefin industry, its progress is invariably closely bound up with the exploitation of new olefine polymerization catalyst, the successful exploitation of each novel catalyst system all can bring the appearance of novel polymeric technique and new type polyolefin product, so that polyethylene is applied in more high-end field.So the new and effective olefin polymerization catalysis that research and development has independent intellectual property right are of great practical significance to development China's oil chemical industry.
Industrial employing at present mainly remain Ziegler-Natta type catalyst (DE Pat 889229 (1953)；IT Pat 536899 (1955) and IT Pat 545332 (1956)；Chem.Rev.,2000,100,1169；Phillips type catalyst (Belg.Pat.530617 (1955)；Chem.Rev.1996,96,3327), also a small amount of metallocene type catalyst (W.Kaminsky, Metalorganic Catalysts for Synthesis and Polymerization, Berlin:Springer,1999).And late transition metal complex catalyst developed in recent years is also due to its high catalysis activity and air stability also result in the great interest of industrial quarters and academia.
1998, Brookhart and Gibson etc. reported pyridine diimine iron, cobalt complex catalyst for ethylene respectively, its structure is for example shown in following formula one [a) J.Am.Chem.Soc., 1998,120,4049；b)Chem.Commun.,1998,849.)]：When such catalyst passes through using different substituent group, ethylene selectivity polymerization or oligomerisation can be made.The research initial to this system finds, under the activation of MAO or MMAO, 2,6 substituted pyridine imine ferrum cobalt complexes show the activity of good catalyzed ethylene polymerization；And only while when substituted, then showing the activity of very high catalyzed ethylene oligomerisation, and gained oligomer obeys Schulz-Flory distribution.After this, the focus of research has concentrated in the change of substituted radical.It is reported that the catalyst of halogenic substituent is carried on pyridine imine aromatic ring, change halogenic substituent can make molecular weight of product scope change to low-molecular-weight oligomer from 377000, when fluoro substituents are contained on part, iron complex shows high oligomerization activity to ethylene, and oligomer obeys Schulz-Flory distribution.When the catalyst that fluorine functional group or Peng Yang functional group are carried on pyridine imine aromatic ring ortho position, the introducing of these groups can increase the stability of catalyst active center, still can have good catalysis activity in pyroreaction, pyridine ring para-position carries the pyridine diimine iron of substituent group, cobalt complex, and its catalysis activity reduces but polymer content raises.
The present inventor place seminar develops the catalyst system (M1, M2, M3) of several new tridentates coordination, achieves good result, they all show excellent performance.Related work has been delivered or has been applied for a patent：Chinese patent ZL 00 132106.4, December 13 2000 applying date, authorized announcement date on January 28th, 2004；Chinese patent ZL 01 1 18568.6, the June 4 calendar year 2001 applying date, authorized announcement date on December 3rd, 2003；Chinese patent ZL 01 1 20553.9, the July 20 calendar year 2001 applying date, authorized announcement date September in 2004 1 day；Chinese Patent Application No. 01124240.X, calendar year 2001 applying date August 17 days；Chinese Patent Application No. 200410086374.6, October 27 2004 applying date；Chinese Patent Application No. 200710119128.X, July 16 2007 applying date.Wherein, 2- benzimidazole -6- amido pyridine iron or 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 or 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.
Two other tooth 8- benzo miaows (oh or thiophene) the azoles quinoline catalyst system M4 of the present inventor place seminar design synthesis and the 2 of three tooth nitrogen dentates, 8- diimine quinoline M5 (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 industrial operation temperature is had well coincide property, have application potential (Organometallics, 2011,30,3,658 3665).
The present inventor have also been devised several classes and contains cycloaliphatic ring N ' N ' the N ferrum of pyridine skeleton or cobalt complex simultaneously.Wherein medium ethylene polymerization activity (the RSC Adv. of the cobalt complex of M6 performance, 2015,5,32720-32729), M7 shows very high ethylene polymerization activity, still keep high ethylene polymerization activity under higher reaction temperatures (50 degree) simultaneously, wherein iron complex catalyzed ethylene polymerization obtains the polyethylene (Organometallics of high molecular, 2012,31,5039-5048), and cobalt complex catalysis obtains the polymerizate (Appl.Catal.A.Gen.2012,447-448) of Narrow Molecular Weight Distribution.M8 also has preferable catalysis activity, and wherein iron complex catalysis obtains the linear polyethylene (Dalton Trans.2014,43,16818-16829) of intermediate molecular weight, and cobalt complex catalysis obtains the polymerizate of Narrow Molecular Weight Distribution.
In current olefin catalytic polymer industry, the Ziegler-Natta catalyst updated and Philips catalyst still play leading effect, and the research for both catalyst is also being carried out always.But both catalyst limitation of itself can not fully meet demand that is growing and raising, people are made not stop to explore other kinds of catalyst, the appearance of wherein metallocene catalyst compensate for the partly deficiency of Ziegler-Natta catalyst and Philips catalyst to a certain extent, so that polyolefinic commercial production is improved and extend, but metallocene catalyst equally faces many problem and shortage in industrial applications.
It is also mainly the exploration for new transition metal catalysts for polyolefinic research outside Current Domestic, the part of design and synthesizing new catalyst becomes the key of research new catalyst.We have had already passed by Ziegler-Natta catalyst system and catalyzing and the chance of metallocene catalyst competition, limited by the encirclement of foreign patent technology.Therefore step up to transition metal olefin polymerization catalyticing research, obtain highly active catalyst system and technique has become China's olefinic polymerization basic research and industrial certainty.
Content of the invention
It is an object of the invention to provide a kind of α, α '-bis-arylimine -2,3:5,6- two (pentamethylene) pyridine iron, cobalt complex catalyst and preparation method and application.
The present invention is achieved through the following technical solutions：
A kind of α, α '-bis-arylimine -2,3:5,6- and two (pentamethylene) pyridine complex catalyst, its structure is shown in formula I：
Wherein, R1、R2、R3、R4、R5Identical or different, it is each independently selected from hydrogen, halogen, nitro, the following radicals optionally being replaced by one or more R '：C1-6Alkyl, C1-6Alkoxyl, C3-10Cycloalkyl, C3-10Cycloalkyl oxy, C6-14Aryl, C6-14Aryloxy group,
Described R ' be each independently selected from halogen, hydroxyl or optionally by one or more R " following groups that replace：C1-6Alkyl, C1-6Alkoxyl, C3-10Cycloalkyl, C3-10Cycloalkyl oxy, C6-14Aryl, C6-14Aryloxy group；
Each R " is independently selected from F, Cl, Br, I, C1-6Alkyl, C1-6Alkyl oxy, C6-14Aryl, C6-14Aryloxy；
M is selected from Fe or Co.
According to the preferred technical solution of the present invention, R1、R2、R3、R4、R5Identical or different, it is each independently selected from hydrogen, halogen, nitro, the following radicals optionally being replaced by one or more R '：C1-3Alkyl, C6-14Aryl,
R ' be each independently selected from halogen, hydroxyl or optionally by one or more R " following groups that replace：C1-6Alkyl, C6-14Aryl.
According to the preferred technical solution of the present invention, R1、R2、R3、R4、R5Identical or different, it is each independently selected from hydrogen, methyl, ethyl, isopropyl, chlorine, bromine, fluorine, nitro, benzhydryl；
M is selected from Fe or Co.
According to the preferred technical solution of the present invention, metal complex of the present invention is selected from any one coordination compound following
Fe-1:R1=Me, R2=H, R3=H, R4=H, R5=Me, M=Fe；
Fe-2:R1=Et, R2=H, R3=H, R4=H, R5=Et, M=Fe；
Fe-3:R1=iPr,R2=H, R3=H, R4=H, R5=iPr, M=Fe；
Fe-4:R1=Me, R2=H, R3=Me, R4=H, R5=Me, M=Fe；
Fe-5:R1=Et, R2=H, R3=Me, R4=H, R5=Et, M=Fe；
Fe-6:R1=Cl, R2=H, R3=H, R4=H, R5=Cl, M=Fe；
Fe-7:R1=Br, R2=H, R3=H, R4=H, R5=Br, M=Fe；
Fe-8:R1=F, R2=H, R3=H, R4=H, R5=F, M=Fe；
Fe-9:R1=NO2,R2=H, R3=H, R4=H, R5=NO2, M=Fe；
Fe-10:R1=Ph2CH,R2=H, R3=Me, R4=H, R5=Ph2CH, M=Fe；
Co-1:R1=Me, R2=H, R3=H, R4=H, R5=Me, M=Co；
Co-2:R1=Et, R2=H, R3=H, R4=H, R5=Et, M=Co；
Co-3:R1=iPr,R2=H, R3=H, R4=H, R5=iPr, M=Co；
Co-4:R1=Me, R2=H, R3=Me, R4=H, R5=Me, M=Co；
Co-5:R1=Et, R2=H, R3=Me, R4=H, R5=Et, M=Co；
Co-6:R1=Cl, R2=H, R3=H, R4=H, R5=Cl, M=Co；
Co-7:R1=Br, R2=H, R3=H, R4=H, R5=Br, M=Co；
Co-8:R1=F, R2=H, R3=H, R4=H, R5=F, M=Co；
Co-9:R1=NO2,R2=H, R3=H, R4=H, R5=NO2, M=Co；
Co-10:R1=Ph2CH,R2=H, R3=Me, R4=H, R5=Ph2CH, M=Co；
Term definition and explanation
Term " C1-6Alkyl " 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 (" C1-4Alkyl "), 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 (" C1-3Alkyl "), such as methyl, ethyl, n-pro-pyl or isopropyl.
Term " C3-10Cycloalkyl " 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 C3-10Cycloalkyl 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 " C6-14Aryl " 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 aromatic6-14Aryl "), 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.
The present invention also provides one kind to prepare described α, α '-bis-arylimine -2,3:5,6- and two (pentamethylene) pyridine complex method it is characterised in that methods described comprises the steps：
In organic solvent, by the compound shown in Formula II, formula III and FeCl2·4H2O or CoCl2Under the protection of nitrogen, back flow reaction obtains.
In above-mentioned steps, in described formula III, R1、R2、R3、R4、R5Definition identical with Formulas I respectively.
In above-mentioned steps, described organic solvent is acetic acid, more preferably glacial acetic acid.In above-mentioned steps, compound II, compound III and FeCl2·4H2O or CoCl2Molar ratio be 1.0-1.5：2.0-3.0:1.0-1.1, specially 1.2:1:2.5.
In above-mentioned steps, it is 10-30mL, specially 15mL that glacial acetic acid uses volume.
In above-mentioned steps, the response time is 2-10 hour, specially 4 hours.
In above-mentioned steps, reaction temperature is 100-150 DEG C, specially 120 DEG C.The reaction process of said method is as shown in Figure 1.
In addition, a kind of present invention also offers carbon monoxide-olefin polymeric for vinyl polymerization；This carbon monoxide-olefin polymeric is included as α shown in the Formulas I of active component, α '-bis-arylimine -2,3:5,6- and two (pentamethylene) pyridine complex, and optional promoter.
According to the present invention, described promoter is selected from MAO (MAO) and one or more of modified methylaluminoxane (MMAO) and diethylaluminum chloride (DEAC)
According to the present invention, described modified MAO is the mixture of trimethyl aluminium and MAO.Described modified MAO can be prepared MAO by such as hydrolyzed trimethylaluminum and prepare：After trimethyl aluminium hydrolysis, the unhydrolysed trimethyl aluminium of residual fraction is referred to as modified MAO with the mixture of MAO.
According to the present invention, the mol ratio of the metallic aluminium in described promoter and the metallic iron in Formulas I is 1000-4000:1, concretely 1000-3000:1、1000-2000:1、2000-4000:1 or 3000-4000:1, more specifically 2000:1.The mol ratio of the metallic aluminium in described promoter and the metallic cobalt in Formulas I is 1000-4000:1, concretely 1000-3000:1、 1000-2000:1、2000-4000:1 or 3000-4000:1, more specifically 2000:1.
Present invention also offers a kind of method preparing polyethylene is it is characterised in that methods described comprises the steps：Under conditions of the carbon monoxide-olefin polymeric that the present invention provides is as catalyst, catalyzed ethylene carries out polyreaction, obtains described polyethylene.
According to the present invention, described promoter is MAO, MMAO；Described polyreaction is carried out under 1atm-10atm, and the temperature of described polyreaction is 10-80 DEG C, for example, 10-50 DEG C, preferably 30-40 DEG C, or is 40-80 DEG C, preferably 60-70 DEG C.
According to the present invention, the polymerization time of described polyreaction is 15min-60min, specially 30-40min.
Described polyreaction is carried out in a solvent；Described solvent is selected from least one in toluene and normal hexane, preferably toluene.
Described polyreaction is carried out in an inert atmosphere；Described inert atmosphere is preferably nitrogen atmosphere.
According to the present invention, the promoter in described iron complex carbon monoxide-olefin polymeric is MAO, and described polyreaction is carried out under normal pressure (1atm), and the polymerization temperature of described polyreaction is 10-50 DEG C, preferably 30-40 DEG C.
According to the present invention, the promoter in described iron complex carbon monoxide-olefin polymeric is MAO, and described polyreaction is carried out under pressurization (1atm-10atm, but do not include 1atm), and the polymerization temperature of described polyreaction is 40-80 DEG C, preferably 60-70 DEG C.
According to the present invention, the promoter in described iron complex carbon monoxide-olefin polymeric is MMAO, and described polyreaction is carried out under normal pressure (1atm), and the polymerization temperature of described polyreaction is 10-50 DEG C, preferably 30-40 DEG C.
According to the present invention, promoter in described iron complex carbon monoxide-olefin polymeric is MMAO, and described polyreaction is carried out under pressurization (1atm-10atm, but do not include 1atm), the polymerization temperature of described polyreaction is 30-70 DEG C, preferably 50-60 DEG C.
According to the present invention, the promoter in described cobalt complex catalyst compositionss is MAO, and described polyreaction is carried out under normal pressure (1atm), and the polymerization temperature of described polyreaction is 10-50 DEG C, preferably 30-40 DEG C.
According to the present invention, the promoter in described cobalt complex catalyst compositionss is MAO, and described polyreaction is carried out under pressurization (1atm-10atm, but do not include 1atm), and the polymerization temperature of described polyreaction is 20-80 DEG C, preferably 30-40 DEG C.
According to the present invention, the promoter in described cobalt complex catalyst compositionss is MMAO and described polyreaction is carried out under normal pressure (1atm), and the polymerization temperature of described polyreaction is 10-50 DEG C, preferably 30-40 DEG C.
According to the present invention, the promoter in described cobalt complex catalyst compositionss is MMAO and described polyreaction is carried out under pressurization (1atm-10atm, but do not include 1atm), and the polymerization temperature of described polyreaction is 20-80 DEG C, preferably 30-40 DEG C.
The present invention has designed and synthesized the α containing N^N^N dentate, α '-bis-arylimine -2,3:5,6- and two (pentamethylene) pyridine complex, this metal complexes is used for catalyzed ethylene polymerization and reacts, and shows very high catalysis activity, respectively reaches 1.28 × 107g·mol-1(Fe)·h-1And 3.69 × 106g·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 the reacting flow chart preparing coordination compound shown in formula I.
Fig. 2 is the crystal structure schematic diagram of coordination compound Fe-1.
Fig. 3 is the crystal structure schematic diagram of coordination compound Co-1.
Specific embodiment
Below by specific embodiment, the present invention will be described, but skilled in the art realises that, the invention is not limited in this.Any improvement made on the basis of the present invention and change, all within protection scope of the present invention.
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 α, α '-two (2,6- dimethyl benzene imines) -2,3:5,6- two (pentamethylene) pyridine conjunction ferrous chloride [Fe-1]
Under nitrogen protection, by 1.2mmol α, α '-diketone -2,3:5,6- and two (pentamethylene) pyridine, 1.0mmol FeCl2·4H2O, 2.5mmol 2,6- dimethylaniline is dissolved in 10mL glacial acetic acid, back flow reaction 4 hours at 120 DEG C.After reaction terminates, it is cooled to room temperature, and adds 30mL absolute ether, continue stirring 2 hours, filter, ether washs, be dried.Obtain blue powder, yield is 74.3%.
Structural identification data is as follows：
FT-IR(cm-1):2940(w),2863(w),1590(m),1552(m),1465(s),1378(w),1340(w),1259(m),1203(s),1166(w),1142(w),1091(m),1036(w),931(w),777(s).
Elementary analysiss C31H35N3FeCl2(576.38), theoretical value：C,64.60；H,6.12；N, 7.29%. measured value:C,64.36；H,5.97；N, 7.14%.
Embodiment 2：Preparation α, α '-two (2,6- diethylbenzene imines) -2,3:5,6- two (pentamethylene) pyridine conjunction ferrous chloride [Fe-2]
Under nitrogen protection, by 1.2mmol α, α '-diketone -2,3:5,6- and two (pentamethylene) pyridine, 1.0mmol FeCl2·4H2O, 2.5mmol 2,6- diethylaniline is dissolved in 10mL glacial acetic acid, back flow reaction 4 hours at 120 DEG C.After reaction terminates, it is cooled to room temperature, and adds 30mL absolute ether, continue stirring 2 hours.Filter, ether washs, be dried.Obtain blue powder, yield is 70.1%.
Structural identification data is as follows：
FT-IR(cm-1):2966(w),2933(w),1577(m),1546(w),1456(s),1375(w),1337(m),1260(m),1209(s),1172(m),1152(m),1059(m),928(w),895(s),773(m).
Elementary analysiss C35H43N3FeCl2(632.49), theoretical value：C,66.46；H,6.85；N, 6.64%. measured value:C,66.33；H,6.56；N, 6.52%.
Embodiment 3：Preparation α, α '-two (2,6- diisopropyl benzene imines) -2,3:5,6- two (pentamethylene) pyridine conjunction ferrous chloride [Fe-3]
Under nitrogen protection, by 1.2mmol α, α '-diketone -2,3:5,6- and two (pentamethylene) pyridine, 1.0mmol FeCl2·4H2O, 2.5mmol 2,6-DIPA is dissolved in 10mL glacial acetic acid, back flow reaction 4 hours at 120 DEG C.After reaction terminates, it is cooled to room temperature, and adds 30mL absolute ether, continue stirring 2 hours.Filter, ether washs, be dried.Obtain blue powder, yield is 61.3%.
Structural identification data is as follows：
FT-IR(cm-1):2941(w),2864(w),1605(m),1553(w),1467(s),1377(w),1339(w),1259(m),1207(m),1166(w),1091(w),1091(w),1035(w),929(w),779(s).
Elementary analysiss C39H51N3FeCl2(688.59), theoretical value：C,68.03；H,7.47；N, 6.10% measured value:C,67.89；H,7.22；N, 5.94%.
Embodiment 4：Preparation α, α '-two (2,4,6- trimethylbenzene imines) -2,3:5,6- two (pentamethylene) pyridine conjunction ferrous chloride [Fe-4]
Under nitrogen protection, by 1.2mmol α, α '-diketone -2,3:5,6- and two (pentamethylene) pyridine, 1.0mmol FeCl2·4H2O, 2.5mmol 2，4，6-trimethyl aniline is dissolved in 10mL glacial acetic acid, back flow reaction 4 hours at 120 DEG C.After reaction terminates, it is cooled to room temperature, and adds 30mL absolute ether, continue stirring 2 hours.Filter, ether washs, be dried.Obtain blue powder, yield is 77.2%.
Structural identification data is as follows：
FT-IR(cm-1):2941(w),2862(w),1607(m),1545(m),1453(s),1380(w),1337(w),1255(m),1212(s),1164(m),1088(w),1039(m),966(w),850(s),740(m).
Elementary analysiss C33H39N3FeCl2(604.43), theoretical value：C,65.57；H,6.50；N, 6.95% measured value:C,65.36；H,6.31；N, 6.57%.
Embodiment 5：Preparation α, α '-two (2,6- diethyl -4- methylbenzene imines) -2,3:5,6- two (pentamethylene) pyridine conjunction ferrous chloride [Fe-5]
Under nitrogen protection, by 1.2mmol α, α '-diketone -2,3:5,6- and two (pentamethylene) pyridine, 1.0mmol FeCl2·4H2O, 2.5mmol 2,6- diethyl -4- monomethylaniline. is dissolved in 10mL glacial acetic acid, back flow reaction 4 hours at 120 DEG C.After reaction terminates, it is cooled to room temperature, and adds 30mL absolute ether, continue stirring 2 hours.Filter, ether washs, be dried.Obtain blue powder, yield is 67.5%.
Structural identification data is as follows：
FT-IR(cm-1):2966(w),2930(w),1605(m),1554(w),1451(s),1374(w),1337(w),1254(m),1196(m),1143(w),1056(m),934(w),808(m),771(s).
Elementary analysiss C37H47N3FeCl2(660.54), theoretical value：C,67.28；H,7.17；N, 6.36% measured value:C,67.01；H,6.99；N, 6.07%.
Embodiment 6：Preparation α, α '-two (2,6- dichloro-benzenes imines) -2,3:5,6- two (pentamethylene) pyridine conjunction ferrous chloride [Fe-6]
Under nitrogen protection, by 1.2mmol α, α '-diketone -2,3:5,6- and two (pentamethylene) pyridine, 1.0mmol FeCl2·4H2O, 2.5mmol 2,6-DCA is dissolved in 10mL glacial acetic acid, back flow reaction 4 hours at 120 DEG C.After reaction terminates, it is cooled to room temperature, and adds 30mL absolute ether, continue stirring 2 hours.Filter, ether washs, be dried.Obtain blue powder, yield is 63.7%.
Structural identification data is as follows：
FT-IR(cm-1):2956(w),2933(w),1610(m),1550(w),1441(s),1377(w),1340(w),1244(m),1190(m),1158(w),1051(m),930(w),800(m),777(s).
Elementary analysiss C27H23N3FeCl6(658.05), theoretical value：C,49.28；H,3.52；N, 6.39% measured value:C,49.00；H,3.47；N, 6.17%.
Embodiment 7：Preparation α, α '-two (2,6- dibromobenzene imines) -2,3:5,6- two (pentamethylene) pyridine conjunction ferrous chloride [Fe-7]
Under nitrogen protection, by 1.2mmol α, α '-diketone -2,3:5,6- and two (pentamethylene) pyridine, 1.0mmol FeCl2·4H2O, 2.5mmol 2,6- dibromo aniline is dissolved in 10mL glacial acetic acid, back flow reaction 4 hours at 120 DEG C.After reaction terminates, it is cooled to room temperature, and adds 30mL absolute ether, continue stirring 2 hours.Filter, ether washs, be dried.Obtain blue powder, yield is 61.3%.
Structural identification data is as follows：FT-IR(cm-1):2954(w),2937(w),1616(m),1555(w),1443(s),1377(w),1341(w),1249(m),1196(m),1154(w),1050(m),936(w),856(m),770(s).
Elementary analysiss C27H23N3Br4FeCl2(835.36), theoretical value：C,38.80；H,2.77；N, 5.03% measured value:C,38.55；H,2.47；N, 5.17%.
Embodiment 8：Preparation α, α '-two (2,6- difluorobenzene imines) -2,3:5,6- two (pentamethylene) pyridine conjunction ferrous chloride [Fe-8]
Under nitrogen protection, by 1.2mmol α, α '-diketone -2,3:5,6- and two (pentamethylene) pyridine, 1.0mmol FeCl2·4H2O, 2.5mmol 2,6- difluoroaniline is dissolved in 10mL glacial acetic acid, back flow reaction 4 hours at 120 DEG C.After reaction terminates, it is cooled to room temperature, and adds 30mL absolute ether, continue stirring 2 hours.Filter, ether washs, be dried.Obtain blue powder, yield is 63.0%.
Structural identification data is as follows：FT-IR(cm-1):2950(w),2923(w),1611(m),1556(w),1445(s),1378(w),1340(w),1250(m),1196(m),1158(w),1088(m),931(w),866(m),798(s).
Elementary analysiss C27H23N3F4FeCl2(592.24), theoretical value：C,54.76；H,3.91；N, 7.10% measured value:C,54.33；H,3.47；N, 7.17%.
Embodiment 9：Preparation α, α '-two (2,6- dinitro benzene imines) -2,3:5,6- two (pentamethylene) pyridine conjunction ferrous chloride [Fe-9]
Under nitrogen protection, by 1.2mmol α, α '-diketone -2,3:5,6- and two (pentamethylene) pyridine, 1.0mmol FeCl2·4H2O, 2.5mmol 2,6- dinitroaniline is dissolved in 10mL glacial acetic acid, back flow reaction 4 hours at 120 DEG C.After reaction terminates, it is cooled to room temperature, and adds 30mL absolute ether, continue stirring 2 hours.Filter, ether washs, be dried.Obtain blue powder, yield is 53.9%.
Structural identification data is as follows：FT-IR(cm-1):2925(w),2910(w),1622(m),1558(w),1431(s),1379(w),1322(w),1241(m),1197(m),1130(w),1056(m),964(w),780(s).
Elementary analysiss C27H23N7O8FeCl2(700.26), theoretical value：C,46.31；H,3.31；N, 14.00% measured value:C,46.33；H,3.17；N, 14.17%.
Embodiment 10：Preparation α, α '-two (2,6- bis- (benzhydryl) benzene imines) -2,3:5,6- two (pentamethylene) pyridine conjunction ferrous chloride [Fe-10]
Under nitrogen protection, by 1.2mmol α, α '-diketone -2,3:5,6- and two (pentamethylene) pyridine, 1.0mmol FeCl2·4H2O, 2.5mmol 2,6- bis- (benzhydryl) aniline is dissolved in 10mL glacial acetic acid, back flow reaction 4 hours at 120 DEG C.After reaction terminates, it is cooled to room temperature, and adds 30mL absolute ether, continue stirring 2 hours.Filter, ether washs, be dried.Obtain blue powder, yield is 76.6%.
Structural identification data is as follows：FT-IR(cm-1):2966(w),2922(w),1602(m),1566(w),1412(s),1370(w),1322(w),1241(m),1188(m),1133(w),1068(m),997(w),967(w),777(s).
Elementary analysiss C79H67N3FeCl2(1185.15), theoretical value：C,80.06；H,5.70；N, 3.55% measured value:C,79.89；H,5.58；N, 3.17%.
Embodiment 11：Preparation α, α '-two (2,6- dimethyl benzene imines) -2,3:5,6- two (pentamethylene) pyridine conjunction cobaltous chloride [Co-1]
Under nitrogen protection, by 1.2mmol α, α '-diketone -2,3:5,6- and two (pentamethylene) pyridine, 1.0mmol CoCl2, 2.5mmol 2,6- dimethylaniline is dissolved in 10mL glacial acetic acid, back flow reaction 4 hours at 120 DEG C.After reaction terminates, it is cooled to room temperature, and adds 30mL absolute ether, continue stirring 2 hours, filter, ether washs, be dried.Obtain brown ceramic powder, yield is 71.2%.
Structural identification data following FT-IR (cm-1):2941(w),2864(w),1605(m),1553(w),1467(s),1377(w),1339(w),1259(m),1207(m),1166(w),1091(w),1091(w),1035(w),929(w),779(s).
Elementary analysiss C31H35N3CoCl2(579.47), theoretical value：C,64.25；H,6.09；N, 7.25%. measured value:C,64.08；H,5.98；N, 7.06%.
Embodiment 12：Preparation α, α '-two (2,6- diethylbenzene imines) -2,3:5,6- two (pentamethylene) pyridine conjunction cobaltous chloride [Co-2]
Under nitrogen protection, by 1.2mmol α, α '-diketone -2,3:5,6- and two (pentamethylene) pyridine, 1.0mmol CoCl2, 2.5mmol 2,6- diethylaniline is dissolved in 10mL glacial acetic acid, back flow reaction 4 hours at 120 DEG C.After reaction terminates, it is cooled to room temperature, and adds 30mL absolute ether, continue stirring 2 hours, filter, ether washs, be dried.Obtain brown ceramic powder, yield is 68.1%.
Structural identification data following FT-IR (cm-1):2966(w),2930(w),1605(m),1554(w),1451(s),1374(w),1337(w),1254(m),1196(m),1143(w),1056(m),934(w),808(m),771(s).
Elementary analysiss C35H43N3CoCl2(635.58), theoretical value：C,66.14；H,6.82；N, 6.61%. measured value:C,66.02；H,6.67；N, 6.41%.
Embodiment 13：Preparation α, α '-two (2,6- diisopropyl benzene imines) -2,3:5,6- two (pentamethylene) pyridine conjunction cobaltous chloride [Co-3]
Under nitrogen protection, by 1.2mmol α, α '-diketone -2,3:5,6- and two (pentamethylene) pyridine, 1.0mmol CoCl2, 2.5mmol 2,6-DIPA is dissolved in 10mL glacial acetic acid, back flow reaction 4 hours at 120 DEG C.After reaction terminates, it is cooled to room temperature, and adds 30mL absolute ether, continue stirring 2 hours, filter, ether washs, be dried.Obtain brown ceramic powder, yield is 59.6%.
Structural identification data following FT-IR (cm-1):2961(w),2866(w),1604(m),1552(w),1460(s),1382(w),1358(w),1253(m),1190(m),1144(w),1050(m),935(w),800(m),766(s).
Elementary analysiss C39H51N3CoCl2(691.68), theoretical value：C,67.72；H,7.43；N, 6.08% measured value:C,67.55；H,7.26；N, 5.96%.
Embodiment 14：Preparation α, α '-two (2,4,6- trimethylbenzene imines) -2,3:5,6- two (pentamethylene) pyridine conjunction cobaltous chloride [Co-4]
Under nitrogen protection, by 1.2mmol α, α '-diketone -2,3:5,6- and two (pentamethylene) pyridine, 1.0mmol CoCl2, 2.5mmol 2，4，6-trimethyl aniline is dissolved in 10mL glacial acetic acid, back flow reaction 4 hours at 120 DEG C.After reaction terminates, it is cooled to room temperature, and adds 30mL absolute ether, continue stirring 2 hours, filter, ether washs, be dried.Obtain brown ceramic powder, yield is 76.5%.
Structural identification data following FT-IR (cm-1):2919(w),2864(w),1606(m),1546(m),1479(s),1450(s),1372(w),1257(m),1216(m),1171(w),1037(w),967(w),856(s).
Elementary analysiss C33H39N3CoCl2(607.52), theoretical value：C,65.24；H,6.47；N, 6.92% measured value:C,65.03；H,6.28；N, 6.80%.
Embodiment 15：Preparation α, α '-two (2,6- diethyl -4- methylbenzene imines) -2,3:5,6- two (pentamethylene) pyridine conjunction cobaltous chloride [Co-5]
Under nitrogen protection, by 1.2mmol α, α '-diketone -2,3:5,6- and two (pentamethylene) pyridine, 1.0mmol CoCl2, 2.5mmol 2,6- diethyl -4- monomethylaniline. is dissolved in 10mL glacial acetic acid, back flow reaction 4 hours at 120 DEG C.After reaction terminates, it is cooled to room temperature, and adds 30mL absolute ether, continue stirring 2 hours, filter, ether washs, be dried.Obtain brown ceramic powder, yield is 66.7%.
Structural identification data following FT-IR (cm-1):2967(w),2930(w),1604(m),1552(w),1457(s),1376(w),1341(w),1257(m),1212(m),1173(w),1058(m),859.
Elementary analysiss C37H47N3CoCl2(663.63), theoretical value：C,66.96；H,7.14；N, 6.33% measured value:C,66.75；H,7.03；N, 6.15%.
Embodiment 16：Preparation α, α '-two (2,6- dichloro-benzenes imines) -2,3:5,6- two (pentamethylene) pyridine conjunction cobaltous chloride [Co-6]
Under nitrogen protection, by 1.2mmol α, α '-diketone -2,3:5,6- and two (pentamethylene) pyridine, 1.0mmol CoCl2, 2.5mmol 2,6-DCA is dissolved in 10mL glacial acetic acid, back flow reaction 4 hours at 120 DEG C.After reaction terminates, it is cooled to room temperature, and adds 30mL absolute ether, continue stirring 2 hours.Filter, ether washs, be dried.Obtain brown ceramic powder, yield is 63.7%.
Structural identification data is as follows：
FT-IR(cm-1):2950(w),2931(w),1616(m),1556(w),1447(s),1377(w),1346(w),1255(m),1191(m),1159(w),1051(m),933(w),820(m),772(s).
Elementary analysiss C27H23N3CoCl6(661.14), theoretical value：C,49.05；H,3.51；N, 6.36% measured value:C,49.17；H,3.40；N, 6.07%.
Embodiment 17：Preparation α, α '-two (2,6- dibromobenzene imines) -2,3:5,6- two (pentamethylene) pyridine conjunction cobaltous chloride [Co-7]
Under nitrogen protection, by 1.2mmol α, α '-diketone -2,3:5,6- and two (pentamethylene) pyridine, 1.0mmol CoCl2, 2.5mmol 2,6- dibromo aniline is dissolved in 10mL glacial acetic acid, back flow reaction 4 hours at 120 DEG C.After reaction terminates, it is cooled to room temperature, and adds 30mL absolute ether, continue stirring 2 hours.Filter, ether washs, be dried.Obtain brown ceramic powder, yield is 60.7%.
Structural identification data is as follows：FT-IR(cm-1):2955(w),2935(w),1610(m),1548(w),1449(s),1371(w),1347(w),1249(m),1190(m),1154(w),1052(m),933(w),859(m),772(s).
Elementary analysiss C27H23N3Br4CoCl2(838.95), theoretical value：C,38.65；H,2.76；N, 5.01% measured value:C,38.35；H,2.40；N, 5.10%.
Embodiment 18：Preparation α, α '-two (2,6- difluorobenzene imines) -2,3:5,6- two (pentamethylene) pyridine conjunction cobaltous chloride [Co-8]
Under nitrogen protection, by 1.2mmol α, α '-diketone -2,3:5,6- and two (pentamethylene) pyridine, 1.0mmol CoCl2, 2.5mmol 2,6- difluoroaniline is dissolved in 10mL glacial acetic acid, back flow reaction 4 hours at 120 DEG C.After reaction terminates, it is cooled to room temperature, and adds 30mL absolute ether, continue stirring 2 hours.Filter, ether washs, be dried.Obtain brown ceramic powder, yield is 59.33%.
Structural identification data is as follows：FT-IR(cm-1):2951(w),2923(w),1615(m),1570(w),1433(s),1372(w),1340(w),1250(m),1191(m),1150(w),1081(m),930(w),868(m),790(s).
Elementary analysiss C27H23N3F4CoCl2(592.24), theoretical value：C,54.74；H,3.89；N, 7.06% measured value:C,54.30；H,3.40；N, 7.10%.
Embodiment 19：Preparation α, α '-two (2,6- dinitro benzene imines) -2,3:5,6- two (pentamethylene) pyridine conjunction cobaltous chloride [Co-9]
Under nitrogen protection, by 1.2mmol α, α '-diketone -2,3:5,6- and two (pentamethylene) pyridine, 1.0mmol CoCl2, 2.5mmol 2,6- dinitroaniline is dissolved in 10mL glacial acetic acid, back flow reaction 4 hours at 120 DEG C.After reaction terminates, it is cooled to room temperature, and adds 30mL absolute ether, continue stirring 2 hours.Filter, ether washs, be dried.Obtain brown ceramic powder, yield is 50.90%.
Structural identification data is as follows：FT-IR(cm-1):2933(w),2921(w),1625(m),1562(w),1430(s),1377(w),1323(w),1247(m),1188(m),1130(w),1056(m),998(w),789(s).
Elementary analysiss C27H23N7O8CoCl2(703.35), theoretical value：C,46.11；H,3.30；N, 13.94% measured value:C,46.23；H,3.37；N, 14.10%.
Embodiment 20：Preparation α, α '-two (2,6- bis- (benzhydryl) benzene imines) -2,3:5,6- two (pentamethylene) pyridine conjunction cobaltous chloride [Co-10]
Under nitrogen protection, by 1.2mmol α, α '-diketone -2,3:5,6- and two (pentamethylene) pyridine, 1.0mmol CoCl2, 2.5mmol 2,6- bis- (benzhydryl) aniline is dissolved in 10mL glacial acetic acid, back flow reaction 4 hours at 120 DEG C.After reaction terminates, it is cooled to room temperature, and adds 30mL absolute ether, continue stirring 2 hours.Filter, ether washs, be dried.Obtain brown ceramic powder, yield is 69.90%.
Structural identification data is as follows：
FT-IR(cm-1):2939(w),2921(w),1615(m),1560(w),1430(s),1367(w),1322(w),1240(m),1188(m),1130(w),1056(m),998(w),780(s).
Elementary analysiss C79H67N3CoCl2(1188.24), theoretical value：C,79.85；H,5.68；N, 3.54% measured value:C,79.78；H,5.37；N, 3.10%.
Embodiment 21, the vinyl polymerization combined using coordination compound Fe-4 and MAO under catalysis normal pressure：
A) under nitrogen protection, the toluene solution toluene solution of the promoter MAO (1.46mol/L) of 15ml toluene and 2.1ml and 15ml having been dissolved coordination compound Fe-4 (3 μm of ol) is added sequentially in 30ml reactor.Now Al/Fe=1000:1.Mechanical agitation starts, and keeps 400 revs/min, when temperature reaches 20 DEG C, is filled with ethylene toward in reactor, polyreaction starts.Keep the ethylene pressure of 1atm at 20 DEG C, stir 30min.With mass fraction 5% hydrochloric acid acidifying ethanol solution neutralization reaction liquid, obtain polymer precipitation, wash for several times with ethanol, vacuum drying to constant weight, 2.55g polymer of weighing to obtain.Polymerization activity：1.70g/mol(Fe)h-1, polymer Tm=125.9 DEG C of (TmFor the melt temperature of polymer, gained is tested by DSC).
B) substantially same a), difference is：Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 3.1ml, makes Al/Fe=1500:1.Polymerization activity：1.82×106g/mol(Fe)h-1, polymer Tm=123.5 DEG C.
C) substantially same a), difference is：Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 4.1ml, makes Al/Fe=2000:1.Polymerization activity：2.01×106g/mol(Fe)h-1, polymer Tm=123.7 DEG C.
D) substantially same a), difference is：Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 5.1ml, makes Al/Fe=2500:1.Polymerization activity：1.61×106g/mol(Fe)h-1, polymer Tm=119.0 DEG C.
E) substantially same a), difference is：Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 6.1ml, makes Al/Fe=3000:1.Polymerization activity：1.11×106g/mol(Fe)h-1, polymer Tm=119.8 DEG C.
F) 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：2.05×106g/mol(Fe)h-1, polymer Tm=121.7 DEG C.
G) substantially same a), difference is：Polymerization temperature is 40 DEG C.Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 4.1ml, makes Al/Fe=2000:1.Polymerization activity：2.09×106g/mol(Fe)h-1, polymer Tm=122.5 DEG C.
H) substantially same a), difference is：Polymerization temperature is 50 DEG C.Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 4.1ml, makes Al/Fe=2000:1.Polymerization activity：2.30×106g/mol(Fe)h-1, polymer Tm=121.7 DEG C.
I) substantially same a), difference is：Polymerization temperature is 60 DEG C.Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 4.1ml, makes Al/Fe=2000:1.Polymerization activity：1.32×106g/mol(Fe)h-1, polymer Tm=119.4 DEG C.
J) substantially same a), difference is：Polymerization temperature is 70 DEG C.Promoter consumption is the toluene solution of the MAO (1.46mol/L) of 4.1ml, makes Al/Fe=2000:1.Polymerization activity：1.01×106g/mol(Fe)h-1, polymer Tm=117.2 DEG C.
Embodiment 22, the vinyl polymerization combined using coordination compound Fe and MAO under catalysis pressurization：
A) basic with embodiment 21 a), difference is the toluene solution of the promoter MAO (1.46mol/L) of 50ml toluene and 4.1ml, and the toluene solution having dissolved catalyst Fe -4 (3 μm of ol) of 50ml is added sequentially in 250ml stainless steel autoclave, Al/Fe=2000:1.When temperature reaches 20 DEG C, it is filled with ethylene toward in autoclave, polyreaction starts.Keep the ethylene pressure of 10atm at 20 DEG C, stir 30min.With 5% hydrochloric acid acidifying ethanol solution neutralization reaction liquid, obtain polymer precipitation, wash for several times with ethanol, vacuum drying to constant weight, 7.70g polymer of weighing to obtain, polymerization activity：5.13×106g/mol(Fe)h-1, polymer Tm=127.8 DEG C of (TmFor the melt temperature of polymer, gained is tested by DSC).
It is b) basic that with embodiment 22, a), difference is：Polymerization temperature is 30 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：7.37×106g/mol(Fe)h-1, polymer Tm=129.0 DEG C.
It is c) basic that with embodiment 22, a), difference is：Polymerization temperature is 40 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：7.86×106g/mol(Fe)h-1, polymer Tm=129.8 DEG C.
It is d) basic that with embodiment 22, a), difference is：Polymerization temperature is 50 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：9.29×106g/mol(Fe)h-1, polymer Tm=127.5 DEG C.
It is e) basic that with embodiment 22, a), difference is：Polymerization temperature is 60 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：12.38×106g/mol(Fe)h-1, polymer Tm=129.1 DEG C.
It is f) basic that with embodiment 22, a), difference is：Polymerization temperature is 70 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：10.96×106g/mol(Fe)h-1, polymer Tm=128.1 DEG C.
It is g) basic that with embodiment 22, a), difference is：Polymerization temperature is 80 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：9.75×106g/mol(Fe)h-1, polymer Tm=128.9 DEG C.
It is h) basic that with embodiment 22, a), difference is：Major catalyst is Fe-1, and polymerization temperature is 60 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：12.81×106g/mol(Fe)h-1, polymer Tm=128.1 DEG C.
It is i) basic that with embodiment 22, a), difference is：Major catalyst is Fe-2, and polymerization temperature is 60 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：11.40×106g/mol(Fe)h-1, polymer Tm=127.4 DEG C.
It is j) basic that with embodiment 22, a), difference is：Major catalyst is Fe-3, and polymerization temperature is 60 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：9.36×106g/mol(Fe)h-1, polymer Tm=130.1 DEG C.
It is k) basic that with embodiment 22, a), difference is：Major catalyst is Fe-5, and polymerization temperature is 60 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：11.74×106g/mol(Fe)h-1, polymer Tm=128.3 DEG C.
It is l) basic that with embodiment 22, a), difference is：Major catalyst is Fe-6, and polymerization temperature is 60 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：10.74×106g/mol(Fe)h-1, polymer Tm=121.3 DEG C.
It is m) basic that with embodiment 22, a), difference is：Major catalyst is Fe-7, and polymerization temperature is 60 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：10.00×106g/mol(Fe)h-1, polymer Tm=121.3 DEG C.
It is n) basic that with embodiment 22, a), difference is：Major catalyst is Fe-8, and polymerization temperature is 60 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：9.87×106g/mol(Fe)h-1, polymer Tm=121.8 DEG C.
It is o) basic that with embodiment 22, a), difference is：Major catalyst is Fe-9, and polymerization temperature is 60 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：9.22×106g/mol(Fe)h-1, polymer Tm=112.6 DEG C.
It is p) basic that with embodiment 22, a), difference is：Major catalyst is Fe-10, and polymerization temperature is 60 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：14.74×106g/mol(Fe)h-1, polymer Tm=123.0 DEG C.
It is q) basic that with embodiment 22, a), difference is：Polymerization temperature is 60 DEG C, and polymerization pressure is 10atm, stirs 15min.Polymerization activity：18.44×106g/mol(Fe)h-1, polymer Tm=127.5 DEG C.
It is r) basic that with embodiment 22, a), difference is：Polymerization temperature is 60 DEG C, and polymerization pressure is 10atm, stirs 45min.Polymerization activity：8.88×106g/mol(Fe)h-1, polymer Tm=127.5 DEG C.
It is s) basic that with embodiment 22, a), difference is：Polymerization temperature is 60 DEG C, and polymerization pressure is 10atm, stirs 60min.Polymerization activity：7.03×106g/mol(Fe)h-1, polymer Tm=129.2 DEG C.
It is t) basic that with embodiment 22, a), difference is：Polymerization temperature is 60 DEG C, and polymerization pressure is 5atm, stirs 30min.Polymerization activity：4.48×106g/mol(Fe)h-1, polymer Tm=125.2 DEG C.
Embodiment 23, the vinyl polymerization combined using coordination compound Fe-4 and MMAO under catalysis normal pressure：
A) under nitrogen protection, the toluene solution toluene solution of the promoter MMAO (2.0mol/L) of 15ml toluene and 1.5ml and 15ml having been dissolved coordination compound Fe4 (3 μm of ol) is added sequentially in 30ml reactor.Now Al/Fe=1000:1.Mechanical agitation starts, and keeps 400 revs/min, when temperature reaches 20 DEG C, is filled with ethylene toward in reactor, polyreaction starts.Keep the ethylene pressure of 1atm at 20 DEG C, stir 30min.With mass fraction 5% hydrochloric acid acidifying ethanol solution neutralization reaction liquid, obtain polymer precipitation, wash for several times with ethanol, vacuum drying to constant weight, 2.41g polymer of weighing to obtain.Polymerization activity：1.61g/mol(Fe)h-1, polymer Tm=122.7 DEG C of (TmFor the melt temperature of polymer, gained is tested by DSC).
It is b) basic that with embodiment 23, a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 2.25ml, makes Al/Fe=1500:1.Polymerization activity：2.01×106g/mol(Fe)h-1, polymer Tm=122.9 DEG C.
It is c) basic that with embodiment 23, a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.0ml, makes Al/Fe=2000:1.Polymerization activity：2.12×106g/mol(Fe)h-1, polymer Tm=129.3 DEG C.
It is d) basic that with embodiment 23, a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.75ml, makes Al/Fe=2500:1.Polymerization activity：1.87×106g/mol(Fe)h-1, polymer Tm=117.2 DEG C.
It is e) basic that with embodiment 23, a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 4.50ml, makes Al/Fe=3000:1.Polymerization activity：1.65×106g/mol(Fe)h-1, polymer Tm=119.8 DEG C.
It is f) basic that with embodiment 23, a), difference is：Polymerization temperature is 30 DEG C.Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.0ml, makes Al/Fe=2000:1.Polymerization activity：2.13×106g/mol(Fe)h-1, polymer Tm=121.3 DEG C.
It is g) basic that with embodiment 23, a), difference is：Polymerization temperature is 40 DEG C.Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.0ml, makes Al/Fe=2000:1.Polymerization activity：2.17×106g/mol(Fe)h-1, polymer Tm=125.0 DEG C.
It is h) basic that with embodiment 23, a), difference is：Polymerization temperature is 50 DEG C.Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.0ml, makes Al/Fe=2000:1.Polymerization activity：2.29×106g/mol(Fe)h-1, polymer Tm=123.9 DEG C.
It is i) basic that with embodiment 23, a), difference is：Polymerization temperature is 60 DEG C.Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.0ml, makes Al/Fe=2000:1.Polymerization activity：1.35×106g/mol(Fe)h-1, polymer Tm=123.4 DEG C.
It is j) basic that with embodiment 23, a), difference is：Polymerization temperature is 70 DEG C.Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.0ml, makes Al/Fe=2000:1.Polymerization activity：0.61×106g/mol(Fe)h-1, polymer Tm=119.3 DEG C.
Embodiment 24, the vinyl polymerization combined using Fe coordination compound and MMAO under catalysis pressurization：
A) basic with embodiment 23 a), difference is the toluene solution of the promoter MMAO (2.0mol/L) of 50ml toluene and 3.0ml, and the toluene solution having dissolved catalyst Fe -4 (3 μm of ol) of 50ml is added sequentially in 250ml stainless steel autoclave, Al/Fe=2000:1.When temperature reaches 20 DEG C, it is filled with ethylene toward in autoclave, polyreaction starts.Keep the ethylene pressure of 10atm at 20 DEG C, stir 30min.With 5% hydrochloric acid acidifying ethanol solution neutralization reaction liquid, obtain polymer precipitation, wash for several times with ethanol, vacuum drying to constant weight, 7.22g polymer of weighing to obtain, polymerization activity：4.81×106g/mol(Fe)h-1, polymer Tm=130.25 DEG C of (TmFor the melt temperature of polymer, gained is tested by DSC).
It is b) basic that with embodiment 24, a), difference is：Polymerization temperature is 30 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：5.14×106g/mol(Fe)h-1, polymer Tm=129.6 DEG C.
It is c) basic that with embodiment 24, a), difference is：Polymerization temperature is 40 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：5.93×106g/mol(Fe)h-1, polymer Tm=127.9 DEG C.
It is d) basic that with embodiment 24, a), difference is：Polymerization temperature is 50 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：6.75×106g/mol(Fe)h-1, polymer Tm=130.9 DEG C.
It is e) basic that with embodiment 24, a), difference is：Polymerization temperature is 60 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：10.13×106g/mol(Fe)h-1, polymer Tm=123.6 DEG C.
It is f) basic that with embodiment 24, a), difference is：Polymerization temperature is 70 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：8.60×106g/mol(Fe)h-1, polymer Tm=130.0 DEG C.
It is g) basic that with embodiment 24, a), difference is：Polymerization temperature is 80 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：7.61×106g/mol(Fe)h-1, polymer Tm=130.3 DEG C.
It is h) basic that with embodiment 24, a), difference is：Major catalyst is Fe1, and polymerization temperature is 60 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：11.71×106g/mol(Fe)h-1, polymer Tm=139.4 DEG C.
It is i) basic that with embodiment 24, a), difference is：Major catalyst is Fe-2, and polymerization temperature is 60 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：10.65×106g/mol(Fe)h-1, polymer Tm=130.7 DEG C.
It is j) basic that with embodiment 24, a), difference is：Major catalyst is Fe-3, and polymerization temperature is 60 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：9.81×106g/mol(Fe)h-1, polymer Tm=130.6 DEG C.
It is k) basic that with embodiment 24, a), difference is：Major catalyst is Fe-5, and polymerization temperature is 60 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：10.07×106g/mol(Fe)h-1, polymer Tm=131.1 DEG C.
It is l) basic that with embodiment 24, a), difference is：Major catalyst is Fe-6, and polymerization temperature is 60 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：10.16×106g/mol(Fe)h-1, polymer Tm=121.1 DEG C.
It is m) basic that with embodiment 24, a), difference is：Major catalyst is Fe-7, and polymerization temperature is 60 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：10.14×106g/mol(Fe)h-1, polymer Tm=131.5 DEG C.
It is n) basic that with embodiment 24, a), difference is：Major catalyst is Fe-8, and polymerization temperature is 60 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：9.22×106g/mol(Fe)h-1, polymer Tm=122.2 DEG C.
It is o) basic that with embodiment 24, a), difference is：Major catalyst is Fe-9, and polymerization temperature is 60 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：9.33×106g/mol(Fe)h-1, polymer Tm=130.2 DEG C.
It is p) basic that with embodiment 24, a), difference is：Major catalyst is Fe-10, and polymerization temperature is 60 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：13.41×106g/mol(Fe)h-1, polymer Tm=121.5 DEG C.
It is q) basic that with embodiment 24, a), difference is：Polymerization temperature is 60 DEG C, and polymerization pressure is 10atm, stirs 15min.Polymerization activity：17.43×106g/mol(Fe)h-1, polymer Tm=131.7 DEG C.
It is r) basic that with embodiment 24, a), difference is：Polymerization temperature is 60 DEG C, and polymerization pressure is 10atm, stirs 45min.Polymerization activity：7.52×106g/mol(Fe)h-1, polymer Tm=131.0 DEG C.
It is s) basic that with embodiment 24, a), difference is：Polymerization temperature is 60 DEG C, and polymerization pressure is 10atm, stirs 60min.Polymerization activity：5.80×106g/mol(Fe)h-1, polymer Tm=132.1 DEG C.
It is t) basic that with embodiment 24, a), difference is：Polymerization temperature is 60 DEG C, and polymerization pressure is 5atm, stirs 30min.Polymerization activity：4.69×106g/mol(Fe)h-1, polymer Tm=129.1 DEG C.
Embodiment 25, the vinyl polymerization combined using coordination compound Co-4 and MMAO under catalysis normal pressure：
A) under nitrogen protection, the toluene solution toluene solution of the promoter MMAO (2.0mol/L) of 15ml toluene and 1.5ml and 15ml having been dissolved coordination compound Co4 (3 μm of ol) is added sequentially in 30ml reactor.Now Al/Fe=1000:1.Mechanical agitation starts, and keeps 400 revs/min, when temperature reaches 20 DEG C, is filled with ethylene toward in reactor, polyreaction starts.Keep the ethylene pressure of 1atm at 20 DEG C, stir 30min.With mass fraction 5% hydrochloric acid acidifying ethanol solution neutralization reaction liquid, obtain polymer precipitation, wash for several times with ethanol, vacuum drying to constant weight, 2.81g polymer of weighing to obtain.Polymerization activity：1.87g/mol(Co)h-1, polymer Tm=125.7 DEG C of (TmFor the melt temperature of polymer, gained is tested by DSC).
It is b) basic that with embodiment 25, a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 2.25ml, makes Al/Co=1500:1.Polymerization activity：2.13×106g/mol(Co)h-1, polymer Tm=125.6 DEG C.
It is c) basic that with embodiment 25, a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.0ml, makes Al/Co=2000:1.Polymerization activity：3.13×106g/mol(Co)h-1, polymer Tm=124.6 DEG C.
It is d) basic that with embodiment 25, a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.75ml, makes Al/Co=2500:1.Polymerization activity：1.87×106g/mol(Co)h-1, polymer Tm=125.7 DEG C.
It is e) basic that with embodiment 25, a), difference is：Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 4.50ml, makes Al/Co=3000:1.Polymerization activity：1.47×106g/mol(Co)h-1, polymer Tm=124.5 DEG C.
It is f) basic that with embodiment 25, a), difference is：Polymerization temperature is 30 DEG C.Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.0ml, makes Al/Co=2000:1.Polymerization activity：3.20×106g/mol(Co)h-1, polymer Tm=122.8 DEG C.
It is g) basic that with embodiment 25, a), difference is：Polymerization temperature is 40 DEG C.Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.0ml, makes Al/Co=2000:1.Polymerization activity：2.87×106g/mol(Co)h-1, polymer Tm=122.1 DEG C.
It is h) basic that with embodiment 25, a), difference is：Polymerization temperature is 50 DEG C.Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.0ml, makes Al/Co=2000:1.Polymerization activity：1.60×106g/mol(Co)h-1, polymer Tm=121.0 DEG C.
It is i) basic that with embodiment 25, a), difference is：Polymerization temperature is 60 DEG C.Promoter consumption is the toluene solution of the MMAO (2.0mol/L) of 3.0ml, makes Al/Co=2000:1.Polymerization activity：1.07×106g/mol(Co)h-1, polymer Tm=119.6 DEG C.
Embodiment 26, the vinyl polymerization combined using Co coordination compound and MMAO under catalysis pressurization：
A) basic with embodiment 25 a), difference is the toluene solution of the promoter MMAO (2.0mol/L) of 50ml toluene and 3.0ml, and the toluene solution having dissolved catalyst Co4 (3 μm of ol) of 50ml is added sequentially in 250ml stainless steel autoclave, Al/Co=2000:1.When temperature reaches 20 DEG C, it is filled with ethylene toward in autoclave, polyreaction starts.Keep the ethylene pressure of 10atm at 20 DEG C, stir 30min.With 5% hydrochloric acid acidifying ethanol solution neutralization reaction liquid, obtain polymer precipitation, wash for several times with ethanol, vacuum drying to constant weight, 2.98g polymer of weighing to obtain, polymerization activity：1.99×106g/mol(Co)h-1, polymer Tm=130.3 DEG C of (TmFor the melt temperature of polymer, gained is tested by DSC).
It is b) basic that with embodiment 26, a), difference is：Polymerization temperature is 30 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：2.14×106g/mol(Co)h-1, polymer Tm=128.7 DEG C.
It is c) basic that with embodiment 26, a), difference is：Polymerization temperature is 40 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：2.45×106g/mol(Co)h-1, polymer Tm=128.9 DEG C.
It is d) basic that with embodiment 26, a), difference is：Polymerization temperature is 50 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：1.91×106g/mol(Co)h-1, polymer Tm=128.9 DEG C.
It is e) basic that with embodiment 26, a), difference is：Polymerization temperature is 60 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：1.39×106g/mol(Co)h-1, polymer Tm=126.8 DEG C.
It is f) basic that with embodiment 26, a), difference is：Polymerization temperature is 70 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：0.88×106g/mol(Co)h-1, polymer Tm=125.7 DEG C.
It is g) basic that with embodiment 26, a), difference is：Polymerization temperature is 80 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：0.62×106g/mol(Co)h-1, polymer Tm=125.1 DEG C.
It is h) basic that with embodiment 26, a), difference is：Major catalyst is Co1, and polymerization temperature is 40 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：2.35×106g/mol(Co)h-1, polymer Tm=126.7 DEG C.
It is i) basic that with embodiment 26, a), difference is：Major catalyst is Co-2, and polymerization temperature is 40 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：2.25×106g/mol(Co)h-1, polymer Tm=132.7 DEG C.
It is j) basic that with embodiment 26, a), difference is：Major catalyst is Co-3, and polymerization temperature is 40 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：1.54×106g/mol(Co)h-1, polymer Tm=134.4 DEG C.
It is k) basic that with embodiment 26, a), difference is：Major catalyst is Co-5, and polymerization temperature is 40 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：2.04×106g/mol(Co)h-1, polymer Tm=131.0 DEG C.
It is l) basic that with embodiment 26, a), difference is：Major catalyst is Co-6, and polymerization temperature is 40 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：2.00×106g/mol(Co)h-1, polymer Tm=119.0 DEG C.
It is m) basic that with embodiment 26, a), difference is：Major catalyst is Co-7, and polymerization temperature is 40 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：1.90×106g/mol(Co)h-1, polymer Tm=123.5 DEG C.
It is n) basic that with embodiment 26, a), difference is：Major catalyst is Co-8, and polymerization temperature is 40 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：1.97×106g/mol(Co)h-1, polymer Tm=126.8 DEG C.
It is o) basic that with embodiment 26, a), difference is：Major catalyst is Co-9, and polymerization temperature is 40 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：1.99×106g/mol(Co)h-1, polymer Tm=126.0 DEG C.
It is p) basic that with embodiment 26, a), difference is：Major catalyst is Co-10, and polymerization temperature is 40 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：3.04×106g/mol(Co)h-1, polymer Tm=130.1 DEG C.
It is q) basic that with embodiment 26, a), difference is：Polymerization temperature is 40 DEG C, and polymerization pressure is 10atm, stirs 15min.Polymerization activity：3.32×106g/mol(Co)h-1, polymer Tm=128.7 DEG C.
It is r) basic that with embodiment 26, a), difference is：Polymerization temperature is 40 DEG C, and polymerization pressure is 10atm, stirs 45min.Polymerization activity：1.82×106g/mol(Co)h-1, polymer Tm=127.4 DEG C.
It is s) basic that with embodiment 26, a), difference is：Polymerization temperature is 40 DEG C, and polymerization pressure is 10atm, stirs 60min.Polymerization activity：1.51×106g/mol(Co)h-1, polymer Tm=126.5 DEG C.
It is t) basic that with embodiment 26, a), difference is：Polymerization temperature is 40 DEG C, and polymerization pressure is 5atm, stirs 30min.Polymerization activity：1.21×106g/mol(Co)h-1, polymer Tm=127.3 DEG C.
Embodiment 27, the vinyl polymerization combined using Co coordination compound and MAO under catalysis pressurization：
A) basic with embodiment 26 a), difference is the toluene solution of the promoter MAO (1.46mol/L) of 50ml toluene and 3.0ml, and the toluene solution having dissolved catalyst Co4 (3 μm of ol) of 50ml is added sequentially in 250ml stainless steel autoclave, Al/Co=2000:1.When temperature reaches 20 DEG C, it is filled with ethylene toward in autoclave, polyreaction starts.Keep the ethylene pressure of 10atm at 20 DEG C, stir 30min.With 5% hydrochloric acid acidifying ethanol solution neutralization reaction liquid, obtain polymer precipitation, wash for several times with ethanol, vacuum drying to constant weight, 4.10g polymer of weighing to obtain, polymerization activity：2.73×106g/mol(Co)h-1, polymer Tm=129.8 DEG C of (TmFor the melt temperature of polymer, gained is tested by DSC).
It is b) basic that with embodiment 27, a), difference is：Polymerization temperature is 30 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：2.82×106g/mol(Co)h-1, polymer Tm=129.2 DEG C.
It is c) basic that with embodiment 27, a), difference is：Polymerization temperature is 40 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：3.69×106g/mol(Co)h-1, polymer Tm=126.3 DEG C.
It is d) basic that with embodiment 27, a), difference is：Polymerization temperature is 50 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：3.40×106g/mol(Co)h-1, polymer Tm=127.3 DEG C.
It is e) basic that with embodiment 27, a), difference is：Polymerization temperature is 60 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：1.85×106g/mol(Co)h-1, polymer Tm=127.1 DEG C.
It is f) basic that with embodiment 27, a), difference is：Polymerization temperature is 70 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：1.28×106g/mol(Co)h-1, polymer Tm=124.8 DEG C.
It is g) basic that with embodiment 27, a), difference is：Polymerization temperature is 80 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：0.96×106g/mol(Co)h-1, polymer Tm=126.2 DEG C.
It is h) basic that with embodiment 27, a), difference is：Major catalyst is Co-1, and polymerization temperature is 40 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：3.42×106g/mol(Co)h-1, polymer Tm=126.2 DEG C.
It is i) basic that with embodiment 27, a), difference is：Major catalyst is Co-2, and polymerization temperature is 40 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：2.88×106g/mol(Co)h-1, polymer Tm=135.0 DEG C.
It is j) basic that with embodiment 27, a), difference is：Major catalyst is Co-3, and polymerization temperature is 40 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：2.31×106g/mol(Co)h-1, polymer Tm=132.78 DEG C.
It is k) basic that with embodiment 27, a), difference is：Major catalyst is Co-5, and polymerization temperature is 40 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：2.91×106g/mol(Co)h-1, polymer Tm=126.5 DEG C.
It is l) basic that with embodiment 27, a), difference is：Major catalyst is Co-6, and polymerization temperature is 40 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：2.94×106g/mol(Co)h-1, polymer Tm=126.7 DEG C.
It is m) basic that with embodiment 27, a), difference is：Major catalyst is Co-7, and polymerization temperature is 40 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：2.67×106g/mol(Co)h-1, polymer Tm=126.0 DEG C.
It is n) basic that with embodiment 27, a), difference is：Major catalyst is Co-8, and polymerization temperature is 40 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：2.66×106g/mol(Co)h-1, polymer Tm=128.2 DEG C.
It is o) basic that with embodiment 27, a), difference is：Major catalyst is Co-9, and polymerization temperature is 40 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：2.88×106g/mol(Co)h-1, polymer Tm=126.1 DEG C.
It is p) basic that with embodiment 27, a), difference is：Major catalyst is Co-10, and polymerization temperature is 40 DEG C, and polymerization pressure is 10atm, stirs 30min.Polymerization activity：3.91×106g/mol(Co)h-1, polymer Tm=128.8 DEG C.
It is q) basic that with embodiment 27, a), difference is：Polymerization temperature is 40 DEG C, and polymerization pressure is 10atm, stirs 15min.Polymerization activity：5.48×106g/mol(Co)h-1, polymer Tm=127.5 DEG C.
It is r) basic that with embodiment 27, a), difference is：Polymerization temperature is 40 DEG C, and polymerization pressure is 10atm, stirs 45min.Polymerization activity：2.68×106g/mol(Co)h-1, polymer Tm=127.1 DEG C.
It is s) basic that with embodiment 27, a), difference is：Polymerization temperature is 40 DEG C, and polymerization pressure is 10atm, stirs 60min.Polymerization activity：2.13×106g/mol(Co)h-1, polymer Tm=126.5 DEG C.
It is t) basic that with embodiment 27, a), difference is：Polymerization temperature is 40 DEG C, and polymerization pressure is 5atm, stirs 30min.Polymerization activity：1.55×106g/mol(Co)h-1, polymer Tm=125.9 DEG C.
Reference examples 1, vinyl polymerization
50ml is dissolved the toluene solution of coordination compound Fe-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 (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.
The carbon monoxide-olefin polymeric being made up of above-mentioned reference examples 1-4, the only compound shown in Formulas I from present invention offer and promoter, under the synergism of two components, just shows as good ethylene polymerization activity.

Claims (11)

1. a kind of α, α '-bis-arylimine -2,3:5,6- and two (pentamethylene) pyridine complex catalyst, its structure is shown in formula I：
Wherein, R1、R2、R3、R4、R5Identical or different, it is each independently selected from hydrogen, halogen, nitro, the following radicals optionally being replaced by one or more R '：C1-6Alkyl, C1-6Alkoxyl, C3-10Cycloalkyl, C3-10Cycloalkyl oxy, C6-14Aryl, C6-14Aryloxy group,
Described R ' be each independently selected from halogen, hydroxyl or optionally by one or more R " following groups that replace：C1-6Alkyl, C1-6Alkoxyl, C3-10Cycloalkyl, C3-10Cycloalkyl oxy, C6-14Aryl, C6-14Aryloxy group；
Each R " is independently selected from F, Cl, Br, I, C1-6Alkyl, C1-6Alkyl oxy, C6-14Aryl, C6-14Aryloxy；
M is selected from Fe or Co.
2. coordination compound according to claim 1 it is characterised in that：R1、R2、R3、R4、R5Identical or different, it is each independently selected from hydrogen, halogen, nitro, the following radicals optionally being replaced by one or more R '：C1-3Alkyl, C6-14Aryl,
R ' be each independently selected from halogen, hydroxyl or optionally by one or more R " following groups that replace：C1-6Alkyl, C6-14Aryl.
3. coordination compound according to claim 1 and 2 it is characterised in that：R1、R2、R3、R4、R5Identical or different, it is each independently selected from hydrogen, methyl, ethyl, isopropyl, chlorine, bromine, fluorine, nitro, benzhydryl；
M is selected from Fe or Co.
4. coordination compound according to claim 1 is it is characterised in that described coordination compound is selected from any one coordination compound following：
Fe-1:R1=Me, R2=H, R3=H, R4=H, R5=Me, M=Fe；
Fe-2:R1=Et, R2=H, R3=H, R4=H, R5=Et, M=Fe；
Fe-3:R1=iPr,R2=H, R3=H, R4=H, R5=iPr, M=Fe；
Fe-4:R1=Me, R2=H, R3=Me, R4=H, R5=Me, M=Fe；
Fe-5:R1=Et, R2=H, R3=Me, R4=H, R5=Et, M=Fe；
Fe-6:R1=Cl, R2=H, R3=H, R4=H, R5=Cl, M=Fe；
Fe-7:R1=Br, R2=H, R3=H, R4=H, R5=Br, M=Fe；
Fe-8:R1=F, R2=H, R3=H, R4=H, R5=F, M=Fe；
Fe-9:R1=NO2,R2=H, R3=H, R4=H, R5=NO2, M=Fe；
Fe-10:R1=Ph2CH,R2=H, R3=Me, R4=H, R5=Ph2CH, M=Fe；
Co-1:R1=Me, R2=H, R3=H, R4=H, R5=Me, M=Co；
Co-2:R1=Et, R2=H, R3=H, R4=H, R5=Et, M=Co；
Co-3:R1=iPr,R2=H, R3=H, R4=H, R5=iPr, M=Co；
Co-4:R1=Me, R2=H, R3=Me, R4=H, R5=Me, M=Co；
Co-5:R1=Et, R2=H, R3=Me, R4=H, R5=Et, M=Co；
Co-6:R1=Cl, R2=H, R3=H, R4=H, R5=Cl, M=Co；
Co-7:R1=Br, R2=H, R3=H, R4=H, R5=Br, M=Co；
Co-8:R1=F, R2=H, R3=H, R4=H, R5=F, M=Co；
Co-9:R1=NO2,R2=H, R3=H, R4=H, R5=NO2；
Co-10:R1=Ph2CH,R2=H, R3=Me, R4=H, R5=Ph2CH, M=Co.
5. a kind of α of any one of claim 1-4, α '-bis-arylimine -2,3:5,6- and two (pentamethylene) pyridine complex method it is characterised in that methods described comprises the steps：In organic solvent, by the compound shown in Formula II, formula III and FeCl2·4H2O or CoCl2Under the protection of nitrogen, back flow reaction obtains.
In described formula III, R1、R2、R3、R4、R5Definition identical with the Formulas I definition of any one of claim 1-3 respectively.
6. method described in 5 is wanted according to right it is characterised in that：Described organic solvent is acetic acid, more have choosing for glacial acetic acid.
Preferably, compound II, compound III and FeCl2·4H2O or CoCl2Molar ratio be 1.0-1.5：2.0-3.0:1.0-1.1, specially 1.2:1:2.5.
Preferably, glacial acetic acid uses volume is 10-30mL, specially 15-20mL.
Preferably, the response time is 2-10 hour, specially 4-6 hour.
Preferably, reaction temperature is 100-150 DEG C, specially 120-140 DEG C.
7. a kind of carbon monoxide-olefin polymeric for vinyl polymerization；This carbon monoxide-olefin polymeric includes the α shown in Formulas I, α '-bis-arylimine -2,3 of any one of claim 1-4 as active component:5,6- and two (pentamethylene) pyridine complex, and optional promoter.
8. carbon monoxide-olefin polymeric according to claim 7 it is characterised in that：Described promoter is chosen in particular from MAO (MAO), at least one in modified methylaluminoxane (MMAO).
Preferably, described modified MAO is the mixture of trimethyl aluminium and MAO.Described modified MAO can be prepared MAO by such as hydrolyzed trimethylaluminum and prepare：After trimethyl aluminium hydrolysis, the unhydrolysed trimethyl aluminium of residual fraction is referred to as modified MAO with the mixture of MAO.
9. the carbon monoxide-olefin polymeric according to claim 7 or 8 is it is characterised in that the metal aluminium element in described promoter is 1000-4000 with the mol ratio of ferrum or cobalt in compound shown in Formulas I:1.
Specifically, metal aluminium element and the mol ratio of ferrum in compound shown in Formulas I are 1000-3000:1；1000-2000:1；2000-4000:1 or 3000-4000:1, more specifically 2000:1.
Metallic aluminium in described promoter is 1000-4000 with the mol ratio of metallic cobalt in compound shown in Formulas I:1, concretely 1000-3000:1；1000-2000:1；2000-4000:1 or 3000-4000:1, more specifically 2000:1.
10. a kind of method preparing polyethylene is it is characterised in that methods described comprises the steps：Under conditions of described in claim 9, carbon monoxide-olefin polymeric is as catalyst, catalyzed ethylene carries out polyreaction, and reaction finishes and obtains described polyethylene.
11. methods according to claim 10 it is characterised in that：
Described promoter is MAO, MMAO；Described polyreaction is carried out under 1atm-10atm, and the temperature of described polyreaction is 10-80 DEG C, for example, 10-50 DEG C, preferably 30-40 DEG C, or is 40-80 DEG C, preferably 60-70 DEG C.
Preferably, the polymerization time of described polyreaction is 15min-60min, specially 30-40min.
Preferably, described polyreaction is carried out in a solvent；Described solvent is selected from least one in toluene and normal hexane, preferably toluene.
Preferably, described polyreaction is carried out in an inert atmosphere；Described inert atmosphere is preferably nitrogen atmosphere.
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CN110407886A (en) * 2018-04-26 2019-11-05 中国科学院化学研究所 One kind prepares the symmetrical heptatomic ring pyridine imine complex of big steric hindrance substituent group, preparation method and the application of polyethylene wax
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CN114149471A (en) * 2020-09-08 2022-03-08 中国科学院化学研究所 Transition metal complex and preparation method and application thereof

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CN114149471A (en) * 2020-09-08 2022-03-08 中国科学院化学研究所 Transition metal complex and preparation method and application thereof
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