CN105273010B - A kind of limitation configuration dinuclear metallocene compounds and the preparation method and application thereof - Google Patents
A kind of limitation configuration dinuclear metallocene compounds and the preparation method and application thereof Download PDFInfo
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Abstract
The present invention provides a kind of limitation configuration dinuclear metallocene compounds and the preparation method and application thereof.Double center CGC that the metallocene compound compound has, it not only has the activity of single-site catalysts, and very easily pass through the length of adjusting carbon bridge, control the electronic environment and space environment of two metal centers, and then regulate and control the molecular weight distribution of polymer, wide distribution polyolefin is produced, scheme provided by the invention has synthetic route short, the advantages of synthesis technology is simple, low industrial cost.
Description
Technical field
The invention belongs to Metallocene catalysts technique fields, and in particular to a kind of limitation configuration dinuclear metallocene compounds and
Preparation method and application.
Background technology
The synthesis of CGC catalyst in 1994 opens the new era of olefin-copolymerization with application study, and DOW companies have applied greatly
Measure the patent of CGC, it is characterised in that containing that can be coordinated nitrogen-atoms on luxuriant ring side chain, the type compound (such as formula III) is suitable for
Homogeneous and supported catalyst ethylene ' alpha '-olefin is copolymerized under high pressure, and activity is 106G Polymer/molMetalh, α-alkene
Hydrocarbon insertion rate is 5-8%mol.
2001, Jerzy Klosin et al. [Jerzy Klosin.Preparation of New Olefin
Polymerization Precatalysts by Facile Derivatization of Imino–EnamidoZrMe3and
HfMe3Complexes [J] 2013,32 (21), pp 6488-6499.] it has studied in detail on indenes ring different substituents and lives to catalysis
Property influence, find introduce hexahydropyridine ring catalytic effect it is best.TobinJ.Marks et al. [TobinJ.Marks.Structure
and dynamics inmetal tetrahydroborates.I.Nuclear magnetic resonance studies
Of zirconiumand hafniumtetrahydroborates [J] .1972,94 (5), pp 1542-1550] synthesize list
Bridged binuclear CGC, and use boron organic matter for co-catalyst, polymerising ethylene 1- octenes, activity reaches 106g Polymer/
MolMetalh, alpha-olefin insertion rate is 7%mol, but with high costs limits its commercial Application.
The monokaryon CGC catalyst of this Si bridgings is always the emphasis of scientists from all over the world's research, to substituent group electronic effect
And stereoeffect is very detailed to the research of its catalytic performance, almost by the monokaryon CGC catalyst of patent protection
The various aspects of the research field are covered, it is difficult to there is big original creativity.But bridge atom changes C by Si1Structure very
Rare report, polyolefin research department of East China University of Science [win .sp perhaps3C1The synthesis of bridging CGC and catalysis ethylene and 1- octenes
Copolymerization application [J] 2012 (12):56-65] develop sp3C1The CGC of bridging, using cheap fulvene be raw material, have synthesis at
The advantages that this is low, synthetic route is short, structure is shown in formula IV：
Bridging type monokaryon metallocene compound is connected with certain abutment, it is a completely new to obtain double-core CGC metallocenes
Research field, moreover, the length by adjusting abutment structure, can effectively control the distance of two metal centers, and then adjust
Its nuclear effect power is controlled, the different polyolefin of molecular weight distribution is generated.The double-core CGC primary structures of document report are shown in Formula V at present：
Researchers have found, due to the influence of nuclear effect, the active higher of double-core CGC, and also alpha-olefin, especially big position
The 1- hexenes of resistance, the insertion rate of 1- octenes increase substantially.But above-mentioned bridging mode, it is to use carbon bridge two CpNSi types
CGC connections, this can undoubtedly increase alpha-olefin insertion steric hindrance；And bridged by Si atoms, step is long, and raw material is expensive.It can
See, using cheap raw material, shorten synthetic route, simplify synthesis technology, reduce cost, improves activity and be inserted into alpha-olefin
Rate is still one of this field urgent problem to be solved.
Invention content
To solve the above problems, the object of the present invention is to provide a kind of limitation configuration dinuclear metallocene compounds, the chemical combination
Double center CGC that object has can easily regulate and control alkene by the modification of substituent group on abutment C and the length of adjusting carbon bridge
The molecular weight distribution of polymer in polymerization.
It is a further object of the present invention to provide the preparation methods of above-mentioned limitation configuration dinuclear metallocene compounds.
It is yet another object of the invention to provide above-mentioned limitation configuration dinuclear metallocene compounds in olefinic polyreaction and
As the application of catalyst in copolyreaction.
In order to achieve the above objectives, the present invention provides a kind of limitation configuration dinuclear metallocene compounds, structure such as Formulas I institutes
Show：
Wherein：R1One kind in hydrogen, methyl and ethyl；
R2One kind in hydrogen, methyl and tertiary butyl；
R3One kind in ethyl, allyl, tertiary butyl, cyclohexyl and phenyl；
R4For C2-C5Saturation or the straight-chain hydrocarbons containing double bond or branched-chain hydrocarbons；
M=Ti or Zr；
X=Cl or Me.
It is to use C in scheme provided by the invention2-C5Straight-chain hydrocarbons or branched-chain hydrocarbons connect two sp3C1Structure C GC, carbon abutment
(carbon at carbon bridge both ends) while methyl or ethyl are introduced on the carbon of cyclopentadienyl ring, methyl, tertiary butyl is introduced on luxuriant ring, in N atoms
Upper introducing ethyl, allyl, tertiary butyl, cyclohexyl or phenyl have obtained a kind of limitation configuration dinuclear metallocene compounds, the change
The structure feature for closing object be by adjusting the length and structure of carbon bridge on the carbon at carbon bridge both ends, can very two gold of convenient control
The distance at category center, and then more preferably regulate and control the distribution of polymer molecular weight.
The steric configuration of limitation configuration dinuclear metallocene compounds provided by the invention is stablized, and sp is used3C1As connection Cp
(cyclopentadienyl) and N atoms limit the rotation of luxuriant ring so that and Cp is relatively fixed with central metal atom position, and
And since the atomic radius of C is less than Si atomic radiuses, the occlusion angle that Cp-M-N is formed is caused to become smaller, the formation of CGC molecules is more increased
The space structure put is conducive to big steric hindrance alpha-olefin and is inserted into.On the other hand, the carbon bridge for connecting two molecules is by connecting two
Sp in molecule3C1, spatially the rear of CpCN polymerization sites, does not influence alkene insertion, therefore have good catalysis completely
Activity and copolymerized ability.
In above-mentioned limitation configuration dinuclear metallocene compounds, it is preferable that it includes following compound：
[(tBuNTiCl2)(η5-C5H4)C(H)]2[(CH2)3]、
[(EtNZrCl2)(η5-C5H4)C(H)]2[(CH2)2]、
[(tBuNTiCl2)(η5-C5H4)C(CH3)]2[(CH2)4]、
[(C6H5NZrCl2)(η5-C5H4)C(CH3)]2[(CH2)3]、
[(tBuNZrCl2)(η5-C5H4)C(H)]2[(CH2)3]、
[(tBuNTiCl2)(η5-C5H4)C(CH3)]2[(CH2)3]、
[(tBuNZrCl2)(η5-C5H4)C(CH3)]2[(CH2)3]、
[(tBuNTiCl2)(η5-MeC5H3)C(H)]2[(CH2)3]、
[(tBuNZrCl2)(η5-MeC5H3)C(H)]2[(CH2)3]、
[(Allyl-NTiCl2)(η5-C5H4)C(H)]2[(CH2)2]、
[(tBuNTiMe2)(η5-C5H4)C(H)]2[(CH2)3]、
[(Allyl-NZrCl2)(η5-C5H4)C(H)]2[(CH2)2]、
[(tBuNZrCl2)(η5-C5H4)C(H)]2[CH=CHC (CH3)]、
[(tBuNTiCl2)(η5-C5H4)C(CH3)]2[CH=CHC (CH3)]、
[(tBuNZrCl2)(η5-C5H4)C(H)]2[C(CH3)=CHC (CH3)2] or
[(tBuNTiCl2)(η5-C5H4)C(CH3)]2[C(CH3)=CHC (CH3)2]。
Invention additionally provides the preparation methods of above-mentioned limitation configuration dinuclear metallocene compounds, wherein this method packet
Include following steps：
(1) so that dicarbonyl compound is reacted with cyclopentadiene, two fulvene of bridging is made；
(2) so that two fulvene of bridging is reacted with amine lithium, double lithium salts of ligand L, the structure such as Formula II institute of the ligand L is made
Show：
(3) double lithium salts of ligand L and n-BuLi is made to be obtained by the reaction four lithium salts, then with MCl4·2THF、MCl4·2Me2S
Or reaction, limitation configuration dinuclear metallocene compounds are made；The MCl4Selected from TiCl4And ZrCl4In one kind.
A kind of synthetic route of limitation configuration dinuclear metallocene compounds provided by the invention is as follows：
The steric configuration that configuration dinuclear metallocene compounds are limited made from the above method is stablized, use double fulvene with
Amine lithium, which reacts, prepares bi-functional ligands, and further with metal complex after lithiumation, obtained double center CGC not only remain list
The activity of center catalyst, and the distance of two metal centers is very easily controlled by the length and structure of adjusting carbon bridge,
And then regulate and control the molecular weight distribution of polymer, the polyolefin of wide distribution can be produced.
In the preparation method of above-mentioned limitation configuration dinuclear metallocene compounds, it is preferable that in step (1), ring penta 2
Alkene uses organic alkali catalyst in being reacted with dicarbonyl compound；
With the gauge of substance, the usage amount of three kinds of substances meets the following conditions：
Cyclopentadiene：Dicarbonyl compound=2.0:1-2.2:1；
Organic base：Dicarbonyl compound=0.05:1-0.1:1；
It is further preferred that the dicarbonyl compound include butanedial, glutaraldehyde, hexandial, dialdehyde in heptan, 2,5- oneself two
Ketone, 2,6- heptadione or 2,7- acetyl caproyls；
It is highly preferred that the organic base includes methylamine, dimethylamine, ethamine, diethylamine, triethylamine or nafoxidine.
In the preparation method of above-mentioned limitation configuration dinuclear metallocene compounds, it is preferable that in step (1), reaction temperature
Degree is -10 DEG C to 30 DEG C, and the reaction time is 1.0-5.0 hours.
In the preparation method of above-mentioned limitation configuration dinuclear metallocene compounds, it is preferable that step (1) includes：In argon gas
Dicarbonyl compound, catalysts and solvents are added in reactor under protection, ring penta 2 is added under the conditions of -10 DEG C to 30 DEG C
Alkene, the reaction was continued 1.0-5.0 hours after adding, post-treated after reaction to obtain two fulvene of the bridging；The solvent is excellent
It is selected as methanol or ethyl alcohol.It is further preferred that the post-processing includes the following steps：Solvent is removed after reaction, and water phase is used
Ether extracts, and is evaporated under reduced pressure after organic phase drying, obtains two fulvene of bridging.It is highly preferred that before removing solvent after the completion of reaction,
Diluted acid can first be added into reaction solution to neutralize organic alkali catalyst, it is preferable to use pH is adjusted to faintly acid by spirit of vinegar；Also may be used
Saturated salt solution is added into reaction solution to reduce solubility of the product in water phase.
In the preparation method of above-mentioned limitation configuration dinuclear metallocene compounds, it is preferable that the step (2) includes：With
Ether or tetrahydrofuran are solvent, and under the conditions of -78 DEG C to 30 DEG C, two fulvene of bridging made from step (1) is instilled amido
The ratio of the tetrahydrofuran or diethyl ether solution of lithium, the amido lithium and the amount of the substance of two fulvene of the bridging is 2.0:1-2.2:
1, it is warming up to reflux temperature after being added dropwise, reacts 3-6 hours, solvent is removed under reduced pressure and obtains solid matter, above-mentioned solid matter
It is post-treated to obtain double lithium salts of ligand L.It is further preferred that the amido lithium includes methyl amine lithium, ethylamine lithium, allyl
Amine lithium, tert-butylamine lithium, cyclo-hexylamine lithium or aniline lithium.It is highly preferred that the step of post-processing, includes：By the solid matter
Hydrolysis, liquid separation, the organic phase after liquid separation is through the dry double lithium salts for being concentrated to give ligand L；Alternatively, by the solid matter alkane
Washing, is then dried to obtain double lithium salts of ligand L, the alkane be preferably pentane or n-hexane (for different products, can
Select then different post processing modes).
In the preparation method of above-mentioned limitation configuration dinuclear metallocene compounds, it is preferable that the step (3) includes：It will
The double lithium salts for the ligand L that step (2) obtains are dissolved in tetrahydrofuran, under the conditions of -78 DEG C to 30 DEG C, instill oneself of butyl lithium
Alkane solution, butyl lithium and the ratio of the amount of the substance of the double lithium salts of ligand L are 4.0:1-4.8:1,20 DEG C are warming up to after being added dropwise extremely
Reflux temperature reacts 3-6 hours, removes solvent and obtains solid, obtained solid is post-treated to obtain four lithium salts of ligand L；
Four lithium salts of above-mentioned ligand L are suspended under the conditions of -80 DEG C to 30 DEG C in ether or tetrahydrofuran solution, MCl is added4,
0 DEG C is warming up to reflux temperature (0 DEG C to the arbitrary temp between reflux temperature), is reacted 3-10 hours, solvent is removed and is consolidated
Body, obtained solid is post-treated to obtain limitation configuration binuclear metallocene catalyst；It is further preferred that the post-processing
Step includes：By solid matter hydrolysis, liquid separation, the organic phase after liquid separation is through dry four lithium salts or the limitation for being concentrated to give ligand L
Configuration dinuclear metallocene compounds；Alternatively, the solid matter is washed with alkane, it is then dried to obtain four lithium salts of ligand L
Or limitation configuration dinuclear metallocene compounds, the alkane be preferably pentane or n-hexane (be directed to different products, it is optional then
Different post processing mode).It is highly preferred that after solid is washed with alkane, recrystallization processing can also be carried out with toluene.
The method provided by the invention for preparing limitation configuration dinuclear metallocene compounds, has synthetic route short, synthesizes work
The advantages of skill is simple, low industrial cost.
The present invention also provides above-mentioned limitation configuration dinuclear metallocene compounds in olefinic polyreaction and copolyreaction
The middle application as catalyst.
In above application, it is preferable that the limitation configuration dinuclear metallocene compounds are as major catalyst, methyl alumina
Alkane makees (MAO) as co-catalyst, and the amount ratio of the substance of major catalyst and co-catalyst is 1：500-2000.Above-mentioned limitation configuration is double
The system of core metallocene compound/MAO has greater activity, the middle alpha-olefin insertion rate of polymer reachable polymerization
7.8mol%.
In the present invention provides a kind of preferred embodiment, using limitation configuration dinuclear metallocene compounds/MAO as
The application mode of catalyst is：In the case where ethylene pressure is 0.1MPa, using toluene or heptane as solvent, limitation configuration double-core is added
The toluene solution of metallocene compound, co-catalyst MAO, the 0.5 hour reaction time at 0 DEG C to 90 DEG C of reaction temperature, catalysis
Vinyl polymerization or ethylene are reacted with alpha-olefin copolymer conjunction.
There are the good limitation configuration dinuclear metallocene compounds for being catalyzed foreground the present invention provides a kind of, the compound
Synthetic route is simple, and product yield is high, and it is easy to isolate and purify, and uses it for catalytic activity height when polymerization, and alpha-olefin insertion rate is high.
Description of the drawings
Fig. 1 is polymer made from embodiment 213C NMR spectras；
Fig. 2 is polymer made from embodiment 313C NMR spectras；
Fig. 3 is polymer made from embodiment 513C NMR spectras；
Fig. 4 is polymer made from embodiment 613C NMR spectras；
Fig. 5 is polymer made from embodiment 813C NMR spectras；
Fig. 6 is polymer made from embodiment 913C NMR spectras；
Fig. 7 is polymer made from embodiment 1113C NMR spectras；
Fig. 8 is polymer made from embodiment 1213C NMR spectras；
Fig. 9 is polymer made from embodiment 1413C NMR spectras；
Figure 10 is polymer made from embodiment 1513C NMR spectras；
Figure 11 is polymer made from comparative example 213C NMR spectras；
Figure 12 is polymer made from comparative example 313C NMR spectras.
Specific implementation mode
In order to which technical characteristic, purpose and the advantageous effect to the present invention are more clearly understood, now to the skill of the present invention
Art scheme carry out it is described further below, but should not be understood as to the present invention can practical range restriction.
Embodiment 1
Present embodiments provide a kind of limitation configuration dinuclear metallocene compounds, the molecular formula of the compound (complex compound 1)
For：[(tBuNTiCl2)(η5-C5H4)C(H)]2[(CH2)3]。
The synthetic route of complex compound 1 is as follows：
The specific preparation process of complex compound 1 is：
(1) argon gas protection under, using methanol as solvent, by glutaraldehyde (100g, 1.0mol), tetrahydro pyrrolidine (3.5g,
It 0.05mol) mixes, reaction bulb is cooled to 0 DEG C, the cyclopentadiene (132g, 2.0mol) newly cracked is slowly instilled, after being added dropwise
Continue to be stirred to react 4 hours, the saturated common salt aqueous solution that spirit of vinegar is added after reaction adjusts pH to faintly acid, steams in rotation
Solvent methanol is removed on hair instrument, water phase is extracted with ether, merges organic phase, is washed with saturation NaCl, anhydrous MgSO4It is dry；It crosses
Filter, is removed under reduced pressure residual solvent, obtains two fulvene of bridging and amounts to 60g, the yield of step (1) is 30%.
(2) two fulvene of bridging (10g, 0.05mol) is dissolved by solvent of ether, under the conditions of -40 DEG C, slowly instills tertiary fourth
The diethyl ether solution of amine lithium (7.0g, 0.1mol) is warming up to reflux temperature after being added dropwise, react 6 hours, is removed under reduced pressure after cooling
Solvent obtains solid matter, and above-mentioned solid is washed with n-hexane, and double lithium salts of ligand L are obtained after dry.
(3) the double lithium salts for the ligand L for obtaining step (2) are added in tetrahydrofuran, so that double lithium salts is suspended, in 0 DEG C of condition
Under be slowly added into molar concentration be 2.0M butyl lithium (50mL, 0.1mol), be then refluxed for 4 hours, solvent, gained be removed under reduced pressure
To solid washed with n-hexane, obtain four lithium salts of ligand L after dry.
Under the conditions of -40 DEG C, four lithium salts (3.6g, 10mmol) of ligand L are taken, cooling tetrahydrofuran is added, stirred, add
Enter TiCl42THF (6.0g, 20mmol), is warmed to room temperature naturally, reacts 4 hours, and solvent is removed under reduced pressure and obtains solid, use just oneself
Alkane is washed, and re crystallization from toluene is then used, and obtains greenish yellow solid, i.e. (the limitation configuration binuclear metallocene chemical combination of complex compound 1
Object).1 mass of complex compound is 4.0g, and fusing point is 195 DEG C, and the molar yield of complex compound 1 is 70%.
Test data,1H NMR (δ, 400MHz, D6C6, 25 DEG C)：1.14 (m, 2H, CH2), 1.42 (s, 18H, N-CMe3),
1.48 (m, 4H, NC-CH2), 4.11 (t, 2H, N-CH), 5.80 (m, 4H, CpH), 6.01 (m, 4H, CpH).
Embodiment 2
It present embodiments provides complex compound 1 made from embodiment 1 as catalyst in homogeneous catalysis vinyl polymerization
Using.
Homogeneous catalysis vinyl polymerization includes the following steps：
By the ethylene gas displacement 3 times of the 100mL autoclaves equipped with magnetic stir bar and gas-guide tube, under nitrogen protection,
Toluene, co-catalyst MAO 2.5mL (1.60M) [Al/M=1000], 2.0 μm of ol complex compounds 1 are sequentially added, control total volume is
100mL is passed through ethylene gas, starts polymerisation at 50 DEG C, maintains ethylene pressure 1.2MPa, is stirred to react 30min, closes
Then gas cylinder, pressure release terminate reaction with 10% acidic alcohol.Polymer is transferred in beaker, is stood overnight, filtering is used in combination
The abundant washing copolymer of ethyl alcohol is dried under vacuum to constant weight at 60 DEG C, weighs polymer quality, polymerization catalyst is obtained after calculating
Activity is 2.3 × 106G polymer/mol Tih, Mw are 16438g/ (gmol-1), PD=Mw/Mn 5.34.From13C
NMR learns and (refers to Fig. 1) by characterization, and obtained polymer does not have branched structure.
Embodiment 3
It present embodiments provides complex compound 1 made from embodiment 1 and is used as catalyst, it is total in homogeneous catalysis ethylene and 1- hexenes
Application in polymerization.
Homogeneous catalysis ethylene includes the following steps with the conjunction of 1- hervene copolymers：
By the ethylene gas displacement 3 times of the 100mL autoclaves equipped with magnetic stir bar and gas-guide tube, under nitrogen protection,
Sequentially add toluene, 1- hexenes 10mL, co-catalyst MAO 2.5mL (1.60M) [Al/M=1000], 2.0 μm of ol complex compounds 1,
Control total volume is 100mL, is passed through ethylene gas, starts polymerisation at 50 DEG C, maintains ethylene pressure 0.3MPa, stirring anti-
30min is answered, gas cylinder is closed, reaction is terminated with 10% acidic alcohol.Polymer is transferred in beaker, is stood overnight, is filtered
The abundant washing copolymer of ethyl alcohol is used in combination, constant weight is dried under vacuum at 60 DEG C, weighs polymer quality, catalyst is obtained after calculating
Polymerization activity 1.1 × 106G polymer/molMh, Mw are 24359g/ (gmol-1), PD=Mw/Mn 5.24.From13C
NMR characterizations are learnt and (refer to Fig. 2), and 1- ahexene contents are 7.8mol% in obtained polymer.
Embodiment 4
Present embodiments provide a kind of limitation configuration dinuclear metallocene compounds, the molecular formula of the compound (complex compound 2)
For：[(tBuNZrCl2)(η5-C5H4)C(H)]2[(CH2)3]。
The preparation process of complex compound 2 is identical as the preparation process of complex compound 1, differs only in and uses ZrCl4Instead of TiCl.On
During stating, the molar yield of gained complex compound 2 is 75%, and the fusing point of complex compound 2 is 187 DEG C.
Test data,1H NMR (δ, 400MHz, D6C6, 25 DEG C)：1.08 (m, 2H, CH2), 1.16 (s, 18H, N-CMe3),
1.39 (m, 4H, NC-CH2), 4.01 (t, 2H, N-CH), 5.64 (m, 4H, CpH), 5.98 (m, 4H, CpH).
Embodiment 5
It present embodiments provides complex compound 2 made from embodiment 4 and is used as catalyst, answering in homogeneous catalysis vinyl polymerization
With.
Homogeneous catalysis vinyl polymerization includes the following steps：
By the ethylene gas displacement 3 times of the 100mL autoclaves with magnetic stir bar, gas-guide tube, under nitrogen protection, according to
Secondary addition toluene, co-catalyst MAO 2.5mL (1.60M) [Al/M=1000], 2.0 μm of ol complex compounds 2, control total volume are
100mL is passed through ethylene gas, starts polymerisation at 50 DEG C, maintains ethylene pressure 1.2MPa, is stirred to react 30min, closes
Then gas cylinder, pressure release terminate reaction with 10% acidic alcohol.Polymer is transferred in beaker, is stood overnight, filtering is used in combination
The abundant washing copolymer of ethyl alcohol is dried under vacuum to constant weight at 50 DEG C, weighs polymer quality, and polymerization catalyst work is calculated
Property be 2.5 × 106G polymer/molTih, Mw are 19455g/ (gmol-1), PD=Mw/Mn 6.26.From13C NMR
Characterization is learnt and (refers to Fig. 3), and obtained polymer does not have branched structure.
Embodiment 6
It present embodiments provides complex compound 2 made from embodiment 4 and is used as catalyst, it is total in homogeneous catalysis ethylene and 1- hexenes
Application in polymerization.
Homogeneous catalysis ethylene includes the following steps with the conjunction of 1- hervene copolymers：
By the ethylene gas displacement 3 times of the 100mL autoclaves with magnetic stir bar, gas-guide tube, under nitrogen protection, according to
Secondary addition toluene, 1- hexenes 10mL, co-catalyst MAO 2.5mL (1.60M) [Al/M=1000], 2.0 μm of ol complex compounds 2, control
Total volume processed is 100mL, is passed through ethylene gas, starts polymerisation at 50 DEG C, maintains ethylene pressure 0.3MPa, is stirred to react
30min closes gas cylinder, and reaction is terminated with 10% acidic alcohol.Polymer is transferred in beaker, is stood overnight, filtering is simultaneously
With the abundant washing copolymer of ethyl alcohol, it is dried under vacuum to constant weight at 50 DEG C, weighs polymer quality, polymerization activity is calculated
2.7×106G polymer/molMh, Mw are 25424g/ (gmol-1), PD=Mw/Mn 6.16.From13C NMR are characterized
Know and (refer to Fig. 4), 1- ahexene contents are 4.4mol% in obtained polymer.
Embodiment 7
Present embodiments provide a kind of limitation configuration dinuclear metallocene compounds, the molecular formula of the compound (complex compound 3)
For：[(tBuNTiMe2)(η5-C5H4)C(H)]2[(CH2)3]。
Under the conditions of -78 DEG C, the double lithium salts (1.15g, 2mmol) and tetrahydrofuran of the ligand L that 1 step 2 of Example obtains
It mixes, is slowly added under stirring conditionnBuLi solution (1.5M, 5.4mL, 8mmol), is slowly ramped to 0 DEG C, it is small to be stirred to react 4
When, solvent is removed under reduced pressure, obtains Tan solid, is washed with pentane, complex compound 3, dark yellow solid are obtained after recrystallization
0.50g, the molar yield 50% of gained complex compound 3.
1H NMR (δ, 400MHz, D6C6, 25 DEG C)：0.40 (s, 12H, TiMe), 1.20 (m, 2H, CH2), 1.51 (s, 18H,
N-CMe3), 1.57 (m, 4H, NC-CH2), 4.27 (t, 2H, N-CH), 5.61 (m, 4H, CpH), 6.10 (m, 4H, CpH).
Embodiment 8
It present embodiments provides complex compound 3 made from embodiment 7 and is used as catalyst, answering in homogeneous catalysis vinyl polymerization
With.
Homogeneous catalysis vinyl polymerization includes the following steps：
By the ethylene gas displacement 3 times of the 100mL autoclaves with magnetic stir bar, gas-guide tube, under nitrogen protection, according to
Secondary addition toluene, co-catalyst MAO 2.5mL (1.60M) [Al/M=1000], 2.0 μm of ol complex compounds 3, control total volume are
100mL is passed through ethylene gas, starts polymerisation at 50 DEG C, maintains ethylene pressure 1.2MPa, is stirred to react 30min, closes
Then gas cylinder, pressure release terminate reaction with 10% acidic alcohol.Polymer is transferred in beaker, is stood overnight, filtering is used in combination
The abundant washing copolymer of ethyl alcohol is dried under vacuum to constant weight at 50 DEG C, weighs polymer quality, and polymerization catalyst work is calculated
Property be 5.7 × 105G polymer/molTih, Mw are 16454g/ (gmol-1), PD=Mw/Mn 4.93.From13C NMR
Characterization is learnt and (refers to Fig. 5), and obtained polymer does not have branched structure.
Embodiment 9
It present embodiments provides complex compound 3 made from embodiment 7 and is used as catalyst, it is total in homogeneous catalysis ethylene and 1- hexenes
Application in polymerization.
Homogeneous catalysis ethylene includes the following steps with the conjunction of 1- hervene copolymers：
By the ethylene gas displacement 3 times of the 100mL autoclaves with magnetic stir bar, gas-guide tube, under nitrogen protection, according to
Secondary addition toluene, 1- hexenes 10mL, co-catalyst MAO 2.5mL (1.60M) [Al/M=1000], 2.0 μm of ol complex compounds 3, control
Total volume processed is 100mL, is passed through ethylene gas, starts polymerisation at 50 DEG C, maintains ethylene pressure 0.3MPa, is stirred to react
30min closes gas cylinder, and reaction is terminated with 10% acidic alcohol.Polymer is transferred in beaker, is stood overnight, filtering is simultaneously
With the abundant washing copolymer of ethyl alcohol, it is dried under vacuum to constant weight at 50 DEG C, weighs polymer quality, polymerization activity is calculated
1.0×106G polymer/molMh, Mw are 23869g/ (gmol-1), PD=Mw/Mn 5.43.From13C NMR are characterized
Know and (refer to Fig. 6), 1- ahexene contents are 4.2mol% in obtained polymer.
Embodiment 10
Present embodiments provide a kind of limitation configuration dinuclear metallocene compounds, the molecular formula of the compound (complex compound 4)
For：[(tBuNTiCl2)(η5-C5H4)C(CH3)]2[(CH2)3]。
The preparation process of complex compound 4 is identical as the preparation process of complex compound 1, differs only in and replaces penta with 2,6- heptadione
Dialdehyde.In the above process, greenish yellow solid (complex compound 4) 3.5g is obtained, fusing point is 210 DEG C, the molar yield of gained complex compound 4
It is 55%.
Test data,1H NMR (δ, 400MHz, D6C6, 25 DEG C)：1.04 (s, 6H, CpCCH3), 1.16 (m, 2H, CH2),
1.40 (s, 18H, N-CMe3), 1.50 (m, 4H, NC-CH2), 5.75 (m, 4H, CpH), 6.04 (m, 4H, CpH).
Embodiment 11
It present embodiments provides complex compound 4 made from embodiment 10 and is used as catalyst, in homogeneous catalysis vinyl polymerization
Using.
Homogeneous catalysis vinyl polymerization includes the following steps：
By the ethylene gas displacement 3 times of the 100mL autoclaves with magnetic stir bar, gas-guide tube, under nitrogen protection, according to
Secondary addition toluene, co-catalyst MAO 2.5mL (1.60M) [Al/M=1000], 2.0 μm of ol complex compounds 4, control total volume are
100mL is passed through ethylene gas, starts polymerisation at 50 DEG C, maintains ethylene pressure 1.2MPa, is stirred to react 30min, closes
Then gas cylinder, pressure release terminate reaction with 10% acidic alcohol.Polymer is transferred in beaker, is stood overnight, filtering is used in combination
The abundant washing copolymer of ethyl alcohol is dried under vacuum to constant weight at 50 DEG C, weighs polymer quality, and polymerization catalyst work is calculated
Property be 1.8 × 106G polymer/molTih, Mw are 17423g/ (gmol-1), PD=Mw/Mn 5.24.From13C NMR
Characterization is learnt and (refers to Fig. 7), and obtained polymer does not have branched structure.
Embodiment 12
It present embodiments provides complex compound 4 made from embodiment 10 and is used as catalyst, in homogeneous catalysis ethylene and 1- hexenes
Application in combined polymerization.
Homogeneous catalysis ethylene includes the following steps with the conjunction of 1- hervene copolymers：
By the ethylene gas displacement 3 times of the 100mL autoclaves with magnetic stir bar, gas-guide tube, under nitrogen protection, according to
Secondary addition toluene, 1- hexenes 10mL, co-catalyst MAO 2.5mL (1.60M) [Al/M=1000], 2.0 μm of ol complex compounds 4, control
Total volume processed is 100mL, is passed through ethylene gas, starts polymerisation at 50 DEG C, maintains ethylene pressure 0.3MPa, is stirred to react
30min closes gas cylinder, and reaction is terminated with 10% acidic alcohol.Polymer is transferred in beaker, is stood overnight, filtering is simultaneously
With the abundant washing copolymer of ethyl alcohol, it is dried under vacuum to constant weight at 50 DEG C, weighs polymer quality, polymerization activity is calculated
2.1×106G polymer/molMh, Mw are 28742g/ (gmol-1), PD=Mw/Mn 6.24.From13C NMR are characterized
Know and (refer to Fig. 8), 1- ahexene contents are 3.9mol% in obtained polymer.
Embodiment 13
Present embodiments provide a kind of limitation configuration dinuclear metallocene compounds, the molecular formula of the compound (complex compound 5)
For：[(Allyl-NTiCl2)(η5-C5H4)C(H)]2[(CH2)3]。
The preparation process of complex compound 5 is identical as the preparation process of complex compound 1, differs only in and replaces tertiary fourth with allyl amine
Base amine.In the above process, yellow solid (complex compound 5) 5.2g is obtained, fusing point is 187 DEG C, and the molar yield of gained complex compound 5 is
66%.
Test data,1H NMR (δ, 400MHz, D6C6, 25 DEG C)：1.20 (m, 2H, CH2), 1.55 (m, 4H, NC-CH2),
3.85 (s, 4H, N-CH2), 4.07 (t, 2H, N-CH), 5.27 (m, 2H, NCCH=), 5.75 (m, 4H, CH2=), 5.85 (m, 4H,
CpH), 6.04 (m, 4H, CpH).
Embodiment 14
It present embodiments provides complex compound 5 made from embodiment 13 and is used as catalyst, in homogeneous catalysis vinyl polymerization
Using.
Polyplant in the present embodiment is with polymerization technique with embodiment 2.Be calculated polymerization catalyst activity be 5.6 ×
106G polymer/mol Tih, Mw are 18634g/ (gmol-1), PD=Mw/Mn 4.83.From13C NMR characterizations are learnt
(referring to Fig. 9), obtained polymer do not have branched structure.
Embodiment 15
It present embodiments provides complex compound 5 made from embodiment 13 and is used as catalyst, in homogeneous catalysis ethylene and 1- hexenes
Application in combined polymerization.
Polyplant in the present embodiment is with polymerization technique with embodiment 3.Polymerization activity 6.4 × 10 is calculated6g
Polymer/mol Mh, Mw are 19452g/ (gmol-1), PD=Mw/Mn 4.86.From13C NMR characterizations, which are learnt, (to be referred to
Figure 10), 1- ahexene contents are 4.8mol% in obtained polymer.
Comparative example 1
Present embodiments provide a kind of known monokaryon limitation configuration metallocene compound, point of the compound (complex compound 6)
Minor is：[(η5-C5H4)C(Me)2(N-t-Bu)TiCl2]。
Specific preparation process：
Take the t-BuNH of 0.80g2(11mmol) is dissolved in 30mLTHF, is slowly added into 6.5mL n-BuLi (1.70mol/
L, 11.50mmol), solution gradually has white opacity appearance, is stirred to react 6, the 6- diformazans of addition (1.17g, 11mmol) after 72h
Base fulvene is stirred to react overnight, adds the n-BuLi (1.7mol/L, 11.5mmol) of 6.5mL and be stirred to react 50h, then
The TiCl of 2.816g is added42THF (10mmol), stirring 50h are obtained olive-green substance, solvent are removed under reduced pressure, is extracted with hexane
(30mL × 2) are taken, hexane is removed under reduced pressure, the solid being mixed to get with 15mL hexanes carefully filters off brown solution, and filter residue and drying obtains
To orange solids 2.19g, as complex compound 6, fusing point is 103-105 DEG C, and gained metal complex molar yield is 48%.
Test data,1H NMR (δ, 500MHz, D6C6, 25 DEG C)：6.40 (s, 1H, CpH), 6.25 (s, 1H, CpH), 6.07
(s, 1H, CpH), 5.81 (s, 1H, CpH), 1.47 (s, 9H, NC (CH3)3), 1.01 (s, 6H, CpC (CH3)2)。
Comparative example 2
It present embodiments provides complex compound 6 made from comparative example 1 and is used as catalyst, answering in homogeneous catalysis vinyl polymerization
With.
Homogeneous catalysis vinyl polymerization includes the following steps：
By the ethylene gas displacement 3 times of the 100mL autoclaves with magnetic stir bar, gas-guide tube, under nitrogen protection, according to
Secondary addition toluene, co-catalyst MAO 2.5mL (1.60M) [Al/M=1000], 2.0 μm of ol complex compounds 5, control total volume are
100mL is passed through ethylene gas, starts polymerisation at 50 DEG C, maintains ethylene pressure 1.2MPa, is stirred to react 30min, closes
Then gas cylinder, pressure release terminate reaction with 10% acidic alcohol.Polymer is transferred in beaker, is stood overnight, filtering is used in combination
The abundant washing copolymer of ethyl alcohol is dried under vacuum to constant weight at 50 DEG C, weighs polymer quality, and polymerization catalyst work is calculated
Property be 1.4 × 106G polymer/molTih, Mw are 12054g/ (gmol-1), PD=Mw/Mn 3.13.From13C NMR
Characterization is learnt and (refers to Figure 11), and obtained polymer does not have branched structure.
Comparative example 3
It present embodiments provides complex compound 6 made from comparative example 1 and is used as catalyst, it is total in homogeneous catalysis ethylene and 1- hexenes
Application in polymerization.
Homogeneous catalysis ethylene includes the following steps with the conjunction of 1- hervene copolymers：
By the ethylene gas displacement 3 times of the 100mL autoclaves with magnetic stir bar, gas-guide tube, under nitrogen protection, according to
Secondary addition toluene, 1- hexenes 10mL, co-catalyst MAO 2.5mL (1.60M) [Al/M=1000], 2.0 μm of ol complex compounds 6, control
Total volume processed is 100mL, is passed through ethylene gas, starts polymerisation at 50 DEG C, maintains ethylene pressure 0.3MPa, is stirred to react
30min closes gas cylinder, and reaction is terminated with 10% acidic alcohol.Polymer is transferred in beaker, is stood overnight, filtering is simultaneously
With the abundant washing copolymer of ethyl alcohol, it is dried under vacuum to constant weight at 50 DEG C, weighs polymer quality, polymerization activity is calculated
2.2×106G polymer/molMh, Mw are 16453g/ (gmol-1), PD=Mw/Mn 3.13.From13C NMR are characterized
Know and (refer to Figure 12), 1- ahexene contents are 3.5mol% in obtained polymer.
The Catalytic data of complex compound 1-6 made from above-described embodiment and comparative example is analyzed into row-column list, concrete outcome is shown in
Table 1 (data of embodiment 2,5,8,11,14 and comparative example 2) and table 2 (data of embodiment 3,6,9,12,15 and comparative example 3)
Content.
1 complex compound of table/MAO catalyzed ethylene polymerization results
| Complex compound | Act.g polymer/mol Ti·h | Mw g/(g·mol-1) | PD=Mw/Mn |
| 1 | 2.3×106 | 16438 | 5.34 |
| 2 | 2.5×106 | 19455 | 6.26 |
| 3 | 5.7×106 | 16454 | 4.93 |
| 4 | 1.8×106 | 17423 | 5.24 |
| 5 | 5.6×106 | 18634 | 4.83 |
| 6 | 1.4×106 | 12054 | 3.13 |
2 complex compounds of table/MAO is catalyzed ethylene/1- hervene copolymer polymerization results
| Complex compound | Act.g polymer/mol Ti·h | Mw g/(g·mol-1) | PD=Mw/Mn |
| 1 | 1.1×106 | 24359 | 5.24 |
| 2 | 2.7×106 | 25424 | 6.16 |
| 3 | 1.0×106 | 23869 | 5.43 |
| 4 | 2.1×106 | 28742 | 6.24 |
| 5 | 6.4×106 | 19452 | 4.86 |
| 6 | 2.2×106 | 16453 | 3.13 |
From table 1, table 2 as can be seen that the complex compound 1-5 catalysis ethylene prepared using method provided by the invention, ethylene/
1- hexene resulting polymers molecular weight distributions have the molecular weight of regulation and control polymer than known monokaryon catalyst (complex compound 6) width
The characteristics of being distributed, producing wide distribution polyolefin.
Claims (16)
1. a kind of limitation configuration dinuclear metallocene compounds, structure are shown in formula I：
Wherein：R1One kind in hydrogen, methyl and ethyl；
R2One kind in hydrogen, methyl and tertiary butyl；
R3One kind in ethyl, allyl, tertiary butyl, cyclohexyl and phenyl；
R4For C2-C5Saturation or the straight-chain hydrocarbons containing double bond or branched-chain hydrocarbons；
M=Ti or Zr；
X=Cl or Me；
Specially following compound：
[(tBuNTiCl2)(η5-C5H4)C(H)]2[(CH2)3]、
[(EtNZrCl2)(η5-C5H4)C(H)]2[(CH2)2]、
[(tBuNTiCl2)(η5-C5H4)C(CH3)]2[(CH2)4]、
[(C6H5NZrCl2)(η5-C5H4)C(CH3)]2[(CH2)3]、
[(tBuNZrCl2)(η5-C5H4)C(H)]2[(CH2)3]、
[(tBuNTiCl2)(η5-C5H4)C(CH3)]2[(CH2)3]、
[(tBuNZrCl2)(η5-C5H4)C(CH3)]2[(CH2)3]、
[(tBuNTiCl2)(η5-MeC5H3)C(H)]2[(CH2)3]、
[(tBuNZrCl2)(η5-MeC5H3)C(H)]2[(CH2)3]、
[(Allyl-NTiCl2)(η5-C5H4)C(H)]2[(CH2)2]、
[(tBuNTiMe2)(η5-C5H4)C(H)]2[(CH2)3]、
[(Allyl-NZrCl2)(η5-C5H4)C(H)]2[(CH2)2]、
[(tBuNZrCl2)(η5-C5H4)C(H)]2[CH=CHC (CH3)]、
[(tBuNTiCl2)(η5-C5H4)C(CH3)]2[CH=CHC (CH3)]、
[(tBuNZrCl2)(η5-C5H4)C(H)]2[C(CH3)=CHC (CH3)2] or
[(tBuNTiCl2)(η5-C5H4)C(CH3)]2[C(CH3)=CHC (CH3)2]。
2. it is a kind of it is described in claim 1 limitation configuration dinuclear metallocene compounds preparation method, wherein this method include with
Lower step：
(1) so that dicarbonyl compound is reacted with cyclopentadiene, two fulvene of bridging is made；
(2) so that two fulvene of bridging is reacted with amine lithium, double lithium salts of ligand L are made, the structure of the ligand L is as shown in Formula II：
(3) double lithium salts of ligand L and n-BuLi is made to be obtained by the reaction four lithium salts, then with MCl4·2THF、MCl4·2Me2S or anti-
It answers, limitation configuration dinuclear metallocene compounds is made；
The MCl4Selected from TiCl4And ZrCl4In one kind.
3. preparation method according to claim 2, wherein in step (1), cyclopentadiene is reacted with dicarbonyl compound
It is middle to use organic alkali catalyst；
With the gauge of substance, the usage amount of three kinds of substances meets the following conditions：
Cyclopentadiene：Dicarbonyl compound=2.0:1-2.2:1；
Organic base：Dicarbonyl compound=0.05:1-0.1:1.
4. preparation method according to claim 2, wherein the dicarbonyl compound include butanedial, glutaraldehyde, oneself two
Aldehyde, dialdehyde in heptan, 2,5- acetyl butyryls, 2,6- heptadione or 2,7- acetyl caproyls.
5. preparation method according to claim 2, wherein the organic base include methylamine, dimethylamine, ethamine, diethylamine,
Triethylamine or nafoxidine.
6. preparation method according to claim 3, wherein in step (1), reaction temperature is -10 DEG C to 30 DEG C, reaction
Time is 1.0-5.0 hours.
7. preparation method according to claim 6, wherein step (1) includes：
Dicarbonyl compound, catalysts and solvents are added in reactor under protection of argon gas, are added under the conditions of -10 DEG C to 30 DEG C
Enter cyclopentadiene, the reaction was continued 1.0-5.0 hours after adding, post-treated after reaction to obtain two fulvene of the bridging.
8. preparation method according to claim 7, wherein in step (1), the solvent is methanol or ethyl alcohol.
9. preparation method according to claim 7, wherein in step (1), the post-processing includes the following steps：Instead
Solvent is removed after answering, water phase is extracted with ether, is evaporated under reduced pressure after organic phase drying, is obtained two fulvene of bridging.
10. preparation method according to claim 2, wherein the step (2) includes：
Using ether or tetrahydrofuran as solvent, under the conditions of -78 DEG C to 30 DEG C, two fulvene of bridging made from step (1) is dripped
Enter the tetrahydrofuran or diethyl ether solution of amido lithium, the ratio of the amido lithium and the amount of the substance of two fulvene of the bridging is 2.0:
1-2.2:1, it is warming up to 20 DEG C after being added dropwise to reflux temperature, reacts 3-6 hours, solvent is removed under reduced pressure and obtains solid matter,
Above-mentioned solid matter is post-treated to obtain double lithium salts of ligand L.
11. preparation method according to claim 10, wherein in step (2), the amido lithium include methyl amine lithium,
Ethylamine lithium, allyl amine lithium, tert-butylamine lithium, cyclo-hexylamine lithium or aniline lithium.
12. preparation method according to claim 10, wherein in step (2), the step of post-processing includes：It will
The solid matter hydrolysis, liquid separation, the organic phase after liquid separation is through the dry double lithium salts for being concentrated to give ligand L；Alternatively, by described solid
Body substance is washed with alkane, is then dried to obtain double lithium salts of ligand L, and the alkane is pentane or n-hexane.
13. preparation method according to claim 2, wherein the step (3) includes：
The double lithium salts for the ligand L that step (2) obtains are dissolved in tetrahydrofuran, under the conditions of -78 DEG C to 30 DEG C, instill butyl
The hexane solution of lithium, butyl lithium and the ratio of the amount of the substance of the double lithium salts of ligand L are 4.0:1-4.8:1, it is warming up to after being added dropwise
20 DEG C, to reflux temperature, are reacted 3-6 hours, are removed solvent and are obtained solid, obtained solid is post-treated to obtain the four of ligand L
Lithium salts；
Four lithium salts of above-mentioned ligand L are suspended under the conditions of -80 DEG C to 30 DEG C in ether or tetrahydrofuran solution, are added
MCl4, 0 DEG C is warming up to reflux temperature, is reacted 3-10 hours, is removed solvent and is obtained solid, obtained solid is post-treated to be obtained
To limitation configuration binuclear metallocene catalyst.
14. preparation method according to claim 13, wherein in step (3), the step of post-processing includes：It will
Solid matter hydrolysis, liquid separation, the organic phase after liquid separation is through dry four lithium salts for being concentrated to give ligand L or limitation configuration double-core cyclopentadienyl gold
Metal catalyst；Alternatively, the solid matter is washed with alkane, four lithium salts or the limitation configuration for being then dried to obtain ligand L are double
Core metallocene catalyst, the alkane are pentane or n-hexane.
15. limitation configuration dinuclear metallocene compounds described in claim 1 are made in olefinic polyreaction and copolyreaction
For the application of catalyst.
16. application according to claim 15, wherein the limitation configuration dinuclear metallocene compounds are as main catalytic
Agent, for methylaluminoxane as co-catalyst, the amount ratio of the substance of major catalyst and co-catalyst is 1：500-2000.
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