CN105273010A - Constrained-configuration dinuclear metallocene, and preparation method and application thereof - Google Patents
Constrained-configuration dinuclear metallocene, and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a constrained-configuration dinuclear metallocene, and a preparation method and application thereof. The metallocene has a two-center CGC (Critical Grid Current), so that not only is the activity of a single-site catalyst realized, but also electronic environments and space environments of the two metal centers are conveniently controlled through adjusting the length of a carbon bridge, the molecular weight distribution of a polymer is further regulated and controlled, and wide-distribution polyolefin is produced. The technical scheme provided by the invention has the advantages of short synthetic route, simple synthetic process and low industrial cost.
Description
Technical field
The invention belongs to Metallocene catalysts technique field, be specifically related to a kind of restriction configuration dinuclear metallocene compounds and preparation method thereof and application.
Background technology
The Synthesis and application research of CGC catalyzer in 1994 opens the New Times of olefin-copolymerization, DOW company has applied for the patent of a large amount of CGC, it is characterized in that on luxuriant ring side chain containing can coordination nitrogen-atoms, the type compound (as formula III) is suitable for homogeneous phase and the under high pressure copolymerization of supported catalyst ethylene ' alpha '-olefin, and activity is 10
6gPolymer/molMetalh, alpha-olefin insertion rate is 5-8%mol.
Calendar year 2001, the people such as JerzyKlosin [JerzyKlosin.PreparationofNewOlefinPolymerizationPrecatal ystsbyFacileDerivatizationofImino – EnamidoZrMe3andHfMe3Complexes [J] 2013,32 (21), pp6488 – 6499.] study different substituents on indenes ring in great detail catalytic activity has been affected, find to introduce hexahydropyridine ring catalytic effect best.The people such as TobinJ.Marks [TobinJ.Marks.Structureanddynamicsinmetaltetrahydroborate s.I.Nuclearmagneticresonancestudiesofzirconiumandhafnium tetrahydroborates [J] .1972,94 (5), pp1542 – 1550] synthesize single bridged binuclear CGC, and use boron organism for promotor, polymerising ethylene 1-octene, activity reaches 10
6gPolymer/molMetalh, alpha-olefin insertion rate is 7%mol, but with high costsly limits its industrial application.
The monokaryon CGC catalyzer of this Si bridging is the emphasis of various countries scientist research always; to substituting group electronic effect and stereoeffect very detailed to the research of its catalytic performance; the all respects of this research field by the monokaryon CGC catalyzer nearly cover of patent protection, are difficult to large original creativity.But bridge atom changes C into by Si
1the rarely found report of structure, polyolefine research department of East China University of Science [is permitted to win .sp
3c
1the synthesis of bridging CGC and catalyzed ethylene and 1-octene copolymer apply [J] 2012 (12): 56-65] develop sp
3c
1the CGC of bridging, uses cheap fulvene to be raw material, and have the advantages such as synthesis cost is low, synthetic route is short, structure is shown in formula IV:
With certain abutment, bridging type monokaryon metallocene compound is coupled together, obtaining double-core CGC metallocene is a brand-new research field, and, by regulating the length of abutment structure, effectively can control the distance of two metal centers, and then it is strong and weak to regulate and control its nuclear effect, produce the polyolefine that molecular weight distribution is different.Formula V is shown in by the double-core CGC primary structure of current bibliographical information:
Investigators find, due to the impact of nuclear effect, the activity of double-core CGC is higher, and alpha-olefin, and particularly the 1-hexene of large steric hindrance, the insertion rate of 1-octene increase substantially.But above-mentioned bridging mode with carbon bridge, the CGC of two CpNSi types is connected, this can increase the steric hindrance that alpha-olefin inserts undoubtedly; And carry out bridge joint by Si atom, step is long, and raw material is expensive.Visible, use cheap raw material, shorten synthetic route, simplify synthesis technique, reduce costs, improve activity and remain one of this area problem demanding prompt solution with alpha-olefin insertion rate.
Summary of the invention
For solving the problem, the object of this invention is to provide a kind of restriction configuration dinuclear metallocene compounds, two center CGC that this compound has, by modification substituent on abutment C and the length regulating carbon bridge, regulate and control the molecular weight distribution of polymkeric substance in olefinic polymerization easily.
Another object of the present invention is to provide the preparation method of above-mentioned restriction configuration dinuclear metallocene compounds.
Another object of the present invention is to provide above-mentioned restriction configuration dinuclear metallocene compounds in olefinic polyreaction and copolyreaction as the application of catalyzer.
For achieving the above object, the invention provides a kind of restriction configuration dinuclear metallocene compounds, its structure is such as formula shown in I:
Wherein: R
1be selected from the one in hydrogen, methyl and ethyl;
R
2be selected from the one in hydrogen, methyl and the tertiary butyl;
R
3be selected from the one in ethyl, allyl group, the tertiary butyl, cyclohexyl and phenyl;
R
4for C
2-C
5saturated or containing double bond straight chain hydrocarbon or branched-chain hydrocarbon;
M=Ti or Zr;
X=Cl or Me.
In scheme provided by the invention for using C
2-C
5straight chain hydrocarbon or branched-chain hydrocarbon connect two sp
3c
1structure C GC, carbon abutment (carbon at carbon bridge two ends) on the carbon of luxuriant ring introduces methyl or ethyl simultaneously, luxuriant ring is introduced methyl, the tertiary butyl, atom N is introduced ethyl, allyl group, the tertiary butyl, cyclohexyl or phenyl, obtain a kind of restriction configuration dinuclear metallocene compounds, the constitutional features of this compound is by regulating length and the structure of carbon bridge on the carbon at carbon bridge two ends, can the distance of very convenient control two metal centers, and then the distribution of better regulation and control polymericular weight.
The sterie configuration of restriction configuration dinuclear metallocene compounds provided by the invention is stablized, and uses sp
3c
1the rotation of luxuriant ring is limited as connection Cp (cyclopentadienyl) and atom N, make Cp relative with central metal atom position fixing, and, atomic radius due to C is less than Si atomic radius, the occlusion angle of causing Cp-M-N to be formed diminishes, CGC molecule forms more open space structure, is conducive to large steric hindrance alpha-olefin and inserts.On the other hand, the carbon bridge of connection two molecules is the sp by connecting in two molecules
3c
1, the spatially rear of CpCN polymerization site, does not affect alkene completely and inserts, therefore have good catalytic activity and copolymerized ability.
In above-mentioned restriction configuration dinuclear metallocene compounds, preferably, it comprises following compound:
[(tBuNTiCl
2)(η
5-C
5H
4)C(H)]
2[(CH
2)
3]、
[(EtNZrCl
2)(η
5-C
5H
4)C(H)]
2[(CH
2)
2]、
[(tBuNTiCl
2)(η
5-C
5H
4)C(CH
3)]
2[(CH
2)
4]、
[(C
6H
5NZrCl
2)(η
5-C
5H
4)C(CH
3)]
2[(CH
2)
3]、
[(tBuNZrCl
2)(η
5-C
5H
4)C(H)]
2[(CH
2)
3]、
[(tBuNTiCl
2)(η
5-C
5H
4)C(CH
3)]
2[(CH
2)
3]、
[(tBuNZrCl
2)(η
5-C
5H
4)C(CH
3)]
2[(CH
2)
3]、
[(tBuNTiCl
2)(η
5-MeC
5H
3)C(H)]
2[(CH
2)
3]、
[(tBuNZrCl
2)(η
5-MeC
5H
3)C(H)]
2[(CH
2)
3]、
[(Allyl-NTiCl
2)(η
5-C
5H
4)C(H)]
2[(CH
2)
2]、
[(tBuNTiMe
2)(η
5-C
5H
4)C(H)]
2[(CH
2)
3]、
[(Allyl-NZrCl
2)(η
5-C
5H
4)C(H)]
2[(CH
2)
2]、
[(tBuNZrCl
2)(η
5-C
5H
4)C(H)]
2[CH＝CHC(CH
3)]、
[(tBuNTiCl
2)(η
5-C
5H
4)C(CH
3)]
2[CH＝CHC(CH
3)]、
[(tBuNZrCl
2) (η
5-C
5h
4) C (H)]
2[C (CH
3)=CHC (CH
3)
2] or
[(tBuNTiCl
2)(η
5-C
5H
4)C(CH
3)]
2[C(CH
3)＝CHC(CH
3)
2]。
Invention additionally provides the preparation method of above-mentioned restriction configuration dinuclear metallocene compounds, wherein, the method comprises the following steps:
(1) dicarbonyl compound and cyclopentadiene is made to react, obtained bridging two fulvene;
(2) make bridging two fulvene and amine lithium react, two lithium salts of obtained ligand L, the structure of described ligand L is such as formula shown in II:
(3) make two lithium salts of ligand L and n-Butyl Lithium be obtained by reacting four lithium salts, then with MCl
42THF, MCl
42Me
2s or reaction, obtained restriction configuration dinuclear metallocene compounds; Described MCl
4be selected from TiCl
4and ZrCl
4in one.
A kind of synthetic route of restriction configuration dinuclear metallocene compounds provided by the invention is as follows:
The sterie configuration of the restriction configuration dinuclear metallocene compounds obtained by aforesaid method is stablized, it adopts two fulvene and amine lithium to react to prepare bi-functional ligands, after lithiumation further with metal complex, the two center CGC obtained, not only remain the activity of single-site catalysts, and very easily by regulating length and the structure of carbon bridge, control the distance of two metal centers, and then the molecular weight distribution of regulation and control polymkeric substance, the polyolefine of wide distribution can be produced.
In the preparation method of above-mentioned restriction configuration dinuclear metallocene compounds, preferably, in step (1), during cyclopentadiene and dicarbonyl compound react, use organic alkali catalyst;
In amount of substance, the usage quantity of three kinds of materials meets the following conditions:
Cyclopentadiene: dicarbonyl compound=2.0:1-2.2:1;
Organic bases: dicarbonyl compound=0.05:1-0.1:1;
Further preferably, described dicarbonyl compound comprise suceinic aldehyde, glutaraldehyde, hexanedial, heptan dialdehyde, 2,5-hexanediones, 2,6-heptadione or 2,7-acetyl caproyl;
More preferably, described organic bases comprises methylamine, dimethylamine, ethamine, diethylamine, triethylamine or Pyrrolidine.
In the preparation method of above-mentioned restriction configuration dinuclear metallocene compounds, preferably, in step (1), temperature of reaction is-10 DEG C to 30 DEG C, and the reaction times is 1.0-5.0 hour.
In the preparation method of above-mentioned restriction configuration dinuclear metallocene compounds, preferably, step (1) comprising: add in reactor by dicarbonyl compound, catalysts and solvents under argon shield, cyclopentadiene is added under-10 DEG C to 30 DEG C conditions, add rear continuation reaction 1.0-5.0 hour, after reaction terminates, obtain described bridging two fulvene through aftertreatment; Described solvent is preferably methyl alcohol or ethanol.Further preferably, described aftertreatment comprises the following steps: except desolventizing after reaction terminates, aqueous phase extracted with diethyl ether, underpressure distillation after organic phase drying, obtains bridging two fulvene.More preferably, after the completion of reaction except before desolventizing, can first add in reaction solution diluted acid with in and organic alkali catalyst, be preferably and use dilute acetic acid that pH is adjusted to slightly acidic; Also saturated aqueous common salt can be added to reduce the solubleness of product in aqueous phase in reaction solution.
In the preparation method of above-mentioned restriction configuration dinuclear metallocene compounds, preferably, described step (2) comprising: with ether or tetrahydrofuran (THF) for solvent, under-78 DEG C to 30 DEG C conditions, by the tetrahydrofuran (THF) of bridging two fulvene instillation amido lithium obtained for step (1) or diethyl ether solution, described amido lithium is 2.0:1-2.2:1 with the ratio of the amount of substance of described bridging two fulvene, reflux temperature is warming up to after dropwising, reaction 3-6 hour, removal of solvent under reduced pressure obtains solid matter, and above-mentioned solid matter obtains two lithium salts of ligand L through aftertreatment.Further preferably, described amido lithium comprises methylamine lithium, ethylamine lithium, allyl amine lithium, TERTIARY BUTYL AMINE lithium, cyclo-hexylamine lithium or aniline lithium.More preferably, the step of described aftertreatment comprises: by described solid matter hydrolysis, separatory, the organic phase drying after separatory concentrates the two lithium salts obtaining ligand L; Or washed by described solid matter alkane, then the dry two lithium salts obtaining ligand L, described alkane is preferably Skellysolve A or normal hexane (for different products, optional then different post processing mode).
In the preparation method of above-mentioned restriction configuration dinuclear metallocene compounds, preferably, described step (3) comprising: two lithium salts of ligand L step (2) obtained are dissolved in tetrahydrofuran (THF), under-78 DEG C to 30 DEG C conditions, the hexane solution of instillation butyllithium, butyllithium is 4.0:1-4.8:1 with the ratio of the amount of substance of the two lithium salts of ligand L, 20 DEG C are warmed up to reflux temperature after dropwising, reaction 3-6 hour, except desolventizing obtains solid, the solid obtained obtains four lithium salts of ligand L through aftertreatment; By four lithium salts of above-mentioned ligand L at-80 DEG C to 30 DEG C condition low suspensions in ether or tetrahydrofuran solution, add MCl
4, be warmed up to 0 DEG C to reflux temperature (arbitrary temp between 0 DEG C to reflux temperature), reaction 3-10 hour, except desolventizing obtains solid, the solid obtained obtains restriction configuration binuclear metallocene catalyzer through aftertreatment; Further preferably, the step of described aftertreatment comprises: by solid matter hydrolysis, separatory, and the organic phase drying after separatory concentrates four lithium salts or restriction configuration dinuclear metallocene compounds that obtain ligand L; Or, described solid matter alkane is washed, then dry four lithium salts or the restriction configuration dinuclear metallocene compounds obtaining ligand L, described alkane is preferably Skellysolve A or normal hexane (for different products, optional then different post processing mode).More preferably, solid, with after alkane washing, can also carry out recrystallization process with toluene.
The method preparing restriction configuration dinuclear metallocene compounds provided by the invention, have synthetic route short, synthesis technique is simple, the advantage of low industrial cost.
Present invention also offers above-mentioned restriction configuration dinuclear metallocene compounds in olefinic polyreaction and copolyreaction as the application of catalyzer.
In above-mentioned application, preferably, described restriction configuration dinuclear metallocene compounds is as Primary Catalysts, and it is promotor that methylaluminoxane makes (MAO), and Primary Catalysts is 1:500-2000 with the amount of substance ratio of promotor.The system of above-mentioned restriction configuration dinuclear metallocene compounds/MAO, has greater activity to polymerization, and the middle alpha-olefin insertion rate of polymkeric substance can reach 7.8mol%.
The invention provides in a kind of preferred implementation, use restriction configuration dinuclear metallocene compounds/MAO as the application mode of catalyzer is: under ethylene pressure is 0.1MPa, with toluene or heptane for solvent, add the toluene solution of restriction configuration dinuclear metallocene compounds, promotor MAO, in the 0.5 hour reaction times at temperature of reaction 0 DEG C to 90 DEG C, catalyzed ethylene polymerization or ethene and alpha-olefin copolymer close and react.
The invention provides a kind of restriction configuration dinuclear metallocene compounds with good catalysis prospect, the synthetic route of this compound is simple, and product yield is high, and separation and purification is easy, and when using it for polymerization, catalytic activity is high, and alpha-olefin insertion rate is high.
Accompanying drawing explanation
Fig. 1 is the obtained polymkeric substance of embodiment 2
13cNMR spectrogram;
Fig. 2 is the obtained polymkeric substance of embodiment 3
13cNMR spectrogram;
Fig. 3 is the obtained polymkeric substance of embodiment 5
13cNMR spectrogram;
Fig. 4 is the obtained polymkeric substance of embodiment 6
13cNMR spectrogram;
Fig. 5 is the obtained polymkeric substance of embodiment 8
13cNMR spectrogram;
Fig. 6 is the obtained polymkeric substance of embodiment 9
13cNMR spectrogram;
Fig. 7 is the obtained polymkeric substance of embodiment 11
13cNMR spectrogram;
Fig. 8 is the obtained polymkeric substance of embodiment 12
13cNMR spectrogram;
Fig. 9 is the obtained polymkeric substance of embodiment 14
13cNMR spectrogram;
Figure 10 is the obtained polymkeric substance of embodiment 15
13cNMR spectrogram;
Figure 11 is the obtained polymkeric substance of comparative example 2
13cNMR spectrogram;
Figure 12 is the obtained polymkeric substance of comparative example 3
13cNMR spectrogram.
Embodiment
In order to there be understanding clearly to technical characteristic of the present invention, object and beneficial effect, existing following detailed description is carried out to technical scheme of the present invention, but can not be interpreted as to of the present invention can the restriction of practical range.
Embodiment 1
Present embodiments provide a kind of restriction configuration dinuclear metallocene compounds, the molecular formula of this compound (complex compound 1) is: [(tBuNTiCl
2) (η
5-C
5h
4) C (H)]
2[(CH
2)
3].
The synthetic route of complex compound 1 is as follows:
The concrete preparation process of complex compound 1 is:
(1) under argon shield; take methyl alcohol as solvent; by glutaraldehyde (100g; 1.0mol), tetrahydro pyrrolidine (3.5g; 0.05mol) mix; reaction flask is cooled to 0 DEG C; slowly instill the cyclopentadiene (132g, 2.0mol) of new cracking, dropwise rear continuation stirring reaction 4 hours; the saturated common salt aqueous solution adding dilute acetic acid after reaction terminates regulates pH to slightly acidic; remove solvent methanol on a rotary evaporator, aqueous phase extracted with diethyl ether, merge organic phase; wash with saturated NaCl, anhydrous MgSO
4dry; Filter, decompression removing residual solvent, obtain bridging two fulvene and amount to 60g, the yield of step (1) is 30%.
(2) take ether as dissolution with solvents bridging two fulvene (10g, 0.05mol), under-40 DEG C of conditions, slowly instill the diethyl ether solution of TERTIARY BUTYL AMINE lithium (7.0g, 0.1mol), after dropwising, be warming up to reflux temperature, react 6 hours, after cooling, removal of solvent under reduced pressure obtains solid matter, by above-mentioned solid n-hexane, obtains two lithium salts of ligand L after drying.
(3) two lithium salts of ligand L step (2) obtained add in tetrahydrofuran (THF), two lithium salts is suspended, butyllithium (the 50mL that volumetric molar concentration is 2.0M is slowly added under 0 DEG C of condition, 0.1mol), then reflux 4 hours, removal of solvent under reduced pressure, the solid n-hexane obtained, obtains four lithium salts of ligand L after drying.
Under-40 DEG C of conditions, get four lithium salts (3.6g, 10mmol) of ligand L, add the tetrahydrofuran (THF) of cooling, stir, add TiCl
42THF (6.0g, 20mmol), rises to room temperature naturally, react 4 hours, removal of solvent under reduced pressure obtains solid, washs with normal hexane, then use re crystallization from toluene, obtain greenish yellow solid, be i.e. complex compound 1 (restriction configuration dinuclear metallocene compounds).Complex compound 1 quality is 4.0g, and fusing point is 195 DEG C, and the molar yield of complex compound 1 is 70%.
Test data,
1hNMR (δ, 400MHz, D
6c
6, 25 DEG C): 1.14 (m, 2H, CH
2), 1.42 (s, 18H, N-CMe
3), 1.48 (m, 4H, NC-CH
2), 4.11 (t, 2H, N-CH), 5.80 (m, 4H, CpH), 6.01 (m, 4H, CpH).
Embodiment 2
Present embodiments provide complex compound 1 obtained for embodiment 1 as the application of catalyzer in homogeneous catalysis vinyl polymerization.
Homogeneous catalysis vinyl polymerization comprises the following steps:
The 100mL autoclave ethylene gas being furnished with magnetic stir bar and airway is replaced 3 times; under nitrogen protection, toluene, promotor MAO2.5mL (1.60M) [Al/M=1000] is added successively, 2.0 μm of ol complex compounds 1; control cumulative volume is 100mL; pass into ethylene gas, at 50 DEG C, start polyreaction, maintain ethylene pressure 1.2MPa; stirring reaction 30min; close gas cylinder, pressure release, then uses the acidic alcohol termination reaction of 10%.Polymkeric substance is transferred in beaker, hold over night, to filter and with the abundant washing copolymer of ethanol, vacuum-drying is to constant weight at 60 DEG C, weigh polymer quality, after calculating, show that polymerization catalyst activity is 2.3 × 10
6gpolymer/molTih, Mw are 16438g/ (gmol
-1), PD=Mw/Mn is 5.34.From
13cNMR characterizes and learns (referring to Fig. 1), and the polymkeric substance obtained does not have branched structure.
Embodiment 3
Present embodiments provide the obtained complex compound 1 of embodiment 1 as catalyzer, the application in homogeneous catalysis ethene and 1-hervene copolymer close.
Homogeneous catalysis ethene and 1-hervene copolymer close and comprise the following steps:
The 100mL autoclave ethylene gas being furnished with magnetic stir bar and airway is replaced 3 times; under nitrogen protection; add toluene, 1-hexene 10mL, promotor MAO2.5mL (1.60M) [Al/M=1000] successively, 2.0 μm of ol complex compounds 1, control cumulative volume is 100mL; pass into ethylene gas; at 50 DEG C, start polyreaction, maintain ethylene pressure 0.3MPa, stirring reaction 30min; close gas cylinder, by the acidic alcohol termination reaction of 10%.Polymkeric substance is transferred in beaker, hold over night, to filter and with the abundant washing copolymer of ethanol, vacuum-drying is to constant weight at 60 DEG C, weigh polymer quality, after calculating, draw polymerization catalyst activity 1.1 × 10
6gpolymer/molMh, Mw are 24359g/ (gmol
-1), PD=Mw/Mn is 5.24.From
13cNMR characterizes and learns (referring to Fig. 2), and in the polymkeric substance obtained, 1-ahexene content is 7.8mol%.
Embodiment 4
Present embodiments provide a kind of restriction configuration dinuclear metallocene compounds, the molecular formula of this compound (complex compound 2) is: [(tBuNZrCl
2) (η
5-C
5h
4) C (H)]
2[(CH
2)
3].
The preparation process of complex compound 2 is identical with the preparation process of complex compound 1, and difference is only to use ZrCl
4replace TiCl.In said process, the molar yield of gained complex compound 2 is 75%, and the fusing point of complex compound 2 is 187 DEG C.
Test data,
1hNMR (δ, 400MHz, D
6c
6, 25 DEG C): 1.08 (m, 2H, CH
2), 1.16 (s, 18H, N-CMe
3), 1.39 (m, 4H, NC-CH
2), 4.01 (t, 2H, N-CH), 5.64 (m, 4H, CpH), 5.98 (m, 4H, CpH).
Embodiment 5
Present embodiments provide the obtained complex compound 2 of embodiment 4 as catalyzer, the application in homogeneous catalysis vinyl polymerization.
Homogeneous catalysis vinyl polymerization comprises the following steps:
100mL autoclave ethylene gas with magnetic stir bar, airway is replaced 3 times; under nitrogen protection, toluene, promotor MAO2.5mL (1.60M) [Al/M=1000] is added successively, 2.0 μm of ol complex compounds 2; control cumulative volume is 100mL; pass into ethylene gas, at 50 DEG C, start polyreaction, maintain ethylene pressure 1.2MPa; stirring reaction 30min; close gas cylinder, pressure release, then uses the acidic alcohol termination reaction of 10%.Transferred to by polymkeric substance in beaker, hold over night, to filter and with the abundant washing copolymer of ethanol, vacuum-drying is to constant weight at 50 DEG C, weigh polymer quality, calculating polymerization catalyst activity is 2.5 × 10
6gpolymer/molTih, Mw are 19455g/ (gmol
-1), PD=Mw/Mn is 6.26.From
13cNMR characterizes and learns (referring to Fig. 3), and the polymkeric substance obtained does not have branched structure.
Embodiment 6
Present embodiments provide the obtained complex compound 2 of embodiment 4 as catalyzer, the application in homogeneous catalysis ethene and 1-hervene copolymer close.
Homogeneous catalysis ethene and 1-hervene copolymer close and comprise the following steps:
100mL autoclave ethylene gas with magnetic stir bar, airway is replaced 3 times; under nitrogen protection; add toluene, 1-hexene 10mL, promotor MAO2.5mL (1.60M) [Al/M=1000] successively, 2.0 μm of ol complex compounds 2, control cumulative volume is 100mL; pass into ethylene gas; at 50 DEG C, start polyreaction, maintain ethylene pressure 0.3MPa, stirring reaction 30min; close gas cylinder, by the acidic alcohol termination reaction of 10%.Polymkeric substance is transferred in beaker, hold over night, to filter and with the abundant washing copolymer of ethanol, vacuum-drying is to constant weight at 50 DEG C, weigh polymer quality, calculate polymerization activity 2.7 × 10
6gpolymer/molMh, Mw are 25424g/ (gmol
-1), PD=Mw/Mn is 6.16.From
13cNMR characterizes and learns (referring to Fig. 4), and in the polymkeric substance obtained, 1-ahexene content is 4.4mol%.
Embodiment 7
Present embodiments provide a kind of restriction configuration dinuclear metallocene compounds, the molecular formula of this compound (complex compound 3) is: [(tBuNTiMe
2) (η
5-C
5h
4) C (H)]
2[(CH
2)
3].
Under-78 DEG C of conditions, two lithium salts (1.15g, 2mmol) of the ligand L that Example 1 step 2 obtains mix with tetrahydrofuran (THF), slowly add under agitation condition
nbuLi solution (1.5M, 5.4mL, 8mmol), is slowly warming up to 0 DEG C, stirring reaction 4 hours, removal of solvent under reduced pressure, obtains Tan solid, washs with Skellysolve A, complex compound 3 is obtained, dark yellow solid 0.50g, the molar yield 50% of gained complex compound 3 after recrystallization.
1HNMR(δ，400MHz，D
6C
6，25℃)：0.40(s，12H，TiMe)，1.20(m，2H，CH
2)，1.51(s，18H，N-CMe
3)，1.57(m，4H，NC-CH
2)，4.27(t，2H，N-CH)，5.61(m，4H，CpH)，6.10(m，4H，CpH)。
Embodiment 8
Present embodiments provide the obtained complex compound 3 of embodiment 7 as catalyzer, the application in homogeneous catalysis vinyl polymerization.
Homogeneous catalysis vinyl polymerization comprises the following steps:
100mL autoclave ethylene gas with magnetic stir bar, airway is replaced 3 times; under nitrogen protection, toluene, promotor MAO2.5mL (1.60M) [Al/M=1000] is added successively, 2.0 μm of ol complex compounds 3; control cumulative volume is 100mL; pass into ethylene gas, at 50 DEG C, start polyreaction, maintain ethylene pressure 1.2MPa; stirring reaction 30min; close gas cylinder, pressure release, then uses the acidic alcohol termination reaction of 10%.Transferred to by polymkeric substance in beaker, hold over night, to filter and with the abundant washing copolymer of ethanol, vacuum-drying is to constant weight at 50 DEG C, weigh polymer quality, calculating polymerization catalyst activity is 5.7 × 10
5gpolymer/molTih, Mw are 16454g/ (gmol
-1), PD=Mw/Mn is 4.93.From
13cNMR characterizes and learns (referring to Fig. 5), and the polymkeric substance obtained does not have branched structure.
Embodiment 9
Present embodiments provide the obtained complex compound 3 of embodiment 7 as catalyzer, the application in homogeneous catalysis ethene and 1-hervene copolymer close.
Homogeneous catalysis ethene and 1-hervene copolymer close and comprise the following steps:
100mL autoclave ethylene gas with magnetic stir bar, airway is replaced 3 times; under nitrogen protection; add toluene, 1-hexene 10mL, promotor MAO2.5mL (1.60M) [Al/M=1000] successively, 2.0 μm of ol complex compounds 3, control cumulative volume is 100mL; pass into ethylene gas; at 50 DEG C, start polyreaction, maintain ethylene pressure 0.3MPa, stirring reaction 30min; close gas cylinder, by the acidic alcohol termination reaction of 10%.Polymkeric substance is transferred in beaker, hold over night, to filter and with the abundant washing copolymer of ethanol, vacuum-drying is to constant weight at 50 DEG C, weigh polymer quality, calculate polymerization activity 1.0 × 10
6gpolymer/molMh, Mw are 23869g/ (gmol
-1), PD=Mw/Mn is 5.43.From
13cNMR characterizes and learns (referring to Fig. 6), and in the polymkeric substance obtained, 1-ahexene content is 4.2mol%.
Embodiment 10
Present embodiments provide a kind of restriction configuration dinuclear metallocene compounds, the molecular formula of this compound (complex compound 4) is: [(tBuNTiCl
2) (η
5-C
5h
4) C (CH
3)]
2[(CH
2)
3].
The preparation process of complex compound 4 is identical with the preparation process of complex compound 1, and difference is only to replace glutaraldehyde with 2,6-heptadione.In said process, obtain greenish yellow solid (complex compound 4) 3.5g, fusing point is 210 DEG C, and the molar yield of gained complex compound 4 is 55%.
Test data,
1hNMR (δ, 400MHz, D
6c
6, 25 DEG C): 1.04 (s, 6H, CpCCH
3), 1.16 (m, 2H, CH
2), 1.40 (s, 18H, N-CMe
3), 1.50 (m, 4H, NC-CH
2), 5.75 (m, 4H, CpH), 6.04 (m, 4H, CpH).
Embodiment 11
Present embodiments provide the obtained complex compound 4 of embodiment 10 as catalyzer, the application in homogeneous catalysis vinyl polymerization.
Homogeneous catalysis vinyl polymerization comprises the following steps:
100mL autoclave ethylene gas with magnetic stir bar, airway is replaced 3 times; under nitrogen protection, toluene, promotor MAO2.5mL (1.60M) [Al/M=1000] is added successively, 2.0 μm of ol complex compounds 4; control cumulative volume is 100mL; pass into ethylene gas, at 50 DEG C, start polyreaction, maintain ethylene pressure 1.2MPa; stirring reaction 30min; close gas cylinder, pressure release, then uses the acidic alcohol termination reaction of 10%.Transferred to by polymkeric substance in beaker, hold over night, to filter and with the abundant washing copolymer of ethanol, vacuum-drying is to constant weight at 50 DEG C, weigh polymer quality, calculating polymerization catalyst activity is 1.8 × 10
6gpolymer/molTih, Mw are 17423g/ (gmol
-1), PD=Mw/Mn is 5.24.From
13cNMR characterizes and learns (referring to Fig. 7), and the polymkeric substance obtained does not have branched structure.
Embodiment 12
Present embodiments provide the obtained complex compound 4 of embodiment 10 as catalyzer, the application in homogeneous catalysis ethene and 1-hervene copolymer close.
Homogeneous catalysis ethene and 1-hervene copolymer close and comprise the following steps:
100mL autoclave ethylene gas with magnetic stir bar, airway is replaced 3 times; under nitrogen protection; add toluene, 1-hexene 10mL, promotor MAO2.5mL (1.60M) [Al/M=1000] successively, 2.0 μm of ol complex compounds 4, control cumulative volume is 100mL; pass into ethylene gas; at 50 DEG C, start polyreaction, maintain ethylene pressure 0.3MPa, stirring reaction 30min; close gas cylinder, by the acidic alcohol termination reaction of 10%.Polymkeric substance is transferred in beaker, hold over night, to filter and with the abundant washing copolymer of ethanol, vacuum-drying is to constant weight at 50 DEG C, weigh polymer quality, calculate polymerization activity 2.1 × 10
6gpolymer/molMh, Mw are 28742g/ (gmol
-1), PD=Mw/Mn is 6.24.From
13cNMR characterizes and learns (referring to Fig. 8), and in the polymkeric substance obtained, 1-ahexene content is 3.9mol%.
Embodiment 13
Present embodiments provide a kind of restriction configuration dinuclear metallocene compounds, the molecular formula of this compound (complex compound 5) is: [(Allyl-NTiCl
2) (η
5-C
5h
4) C (H)]
2[(CH
2)
3].
The preparation process of complex compound 5 is identical with the preparation process of complex compound 1, and difference is only to replace tert-butylamine with allyl amine.In said process, obtain yellow solid (complex compound 5) 5.2g, fusing point is 187 DEG C, and the molar yield of gained complex compound 5 is 66%.
Test data,
1hNMR (δ, 400MHz, D
6c
6, 25 DEG C): 1.20 (m, 2H, CH
2), 1.55 (m, 4H, NC-CH
2), 3.85 (s, 4H, N-CH
2), 4.07 (t, 2H, N-CH), 5.27 (m, 2H, NCCH=), 5.75 (m, 4H, CH
2=), 5.85 (m, 4H, CpH), 6.04 (m, 4H, CpH).
Embodiment 14
Present embodiments provide the obtained complex compound 5 of embodiment 13 as catalyzer, the application in homogeneous catalysis vinyl polymerization.
Poly-unit in the present embodiment and polymerization technique are with embodiment 2.Calculating polymerization catalyst activity is 5.6 × 10
6gpolymer/molTih, Mw are 18634g/ (gmol
-1), PD=Mw/Mn is 4.83.From
13cNMR characterizes and learns (referring to Fig. 9), and the polymkeric substance obtained does not have branched structure.
Embodiment 15
Present embodiments provide the obtained complex compound 5 of embodiment 13 as catalyzer, the application in homogeneous catalysis ethene and 1-hervene copolymer close.
Poly-unit in the present embodiment and polymerization technique are with embodiment 3.Calculate polymerization activity 6.4 × 10
6gpolymer/molMh, Mw are 19452g/ (gmol
-1), PD=Mw/Mn is 4.86.From
13cNMR characterizes and learns (referring to Figure 10), and in the polymkeric substance obtained, 1-ahexene content is 4.8mol%.
Comparative example 1
Present embodiments provide a kind of known monokaryon restriction configuration metallocene compound, the molecular formula of this compound (complex compound 6) is: [(η
5-C
5h
4) C (Me)
2(N-t-Bu) TiCl
2].
Concrete preparation process:
Get the t-BuNH of 0.80g
2(11mmol) be dissolved in 30mLTHF, slowly add 6.5mLn-BuLi (1.70mol/L, 11.50mmol), solution gradually adularescent muddiness occurs, adds (1.17g after stirring reaction 72h, 11mmol) 6,6-dimethyl fulvene, stirring reaction spends the night, then adds the n-BuLi (1.7mol/L of 6.5mL, 11.5mmol) and stirring reaction 50h, the TiCl of 2.816g is then added
42THF (10mmol), stir 50h and obtain olive-green material, removal of solvent under reduced pressure, with hexane extraction (30mL × 2), decompression removing hexane, with the solid that 15mL hexane is mixed to get, careful elimination brown solution, filter residue and drying obtains orange solids 2.19g, is complex compound 6, fusing point is 103-105 DEG C, and gained metal complex molar yield is 48%.
Test data,
1hNMR (δ, 500MHz, D
6c
6, 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 (CH
3)
3), 1.01 (s, 6H, CpC (CH
3)
2).
Comparative example 2
Present embodiments provide the obtained complex compound 6 of comparative example 1 as catalyzer, the application in homogeneous catalysis vinyl polymerization.
Homogeneous catalysis vinyl polymerization comprises the following steps:
100mL autoclave ethylene gas with magnetic stir bar, airway is replaced 3 times; under nitrogen protection, toluene, promotor MAO2.5mL (1.60M) [Al/M=1000] is added successively, 2.0 μm of ol complex compounds 5; control cumulative volume is 100mL; pass into ethylene gas, at 50 DEG C, start polyreaction, maintain ethylene pressure 1.2MPa; stirring reaction 30min; close gas cylinder, pressure release, then uses the acidic alcohol termination reaction of 10%.Transferred to by polymkeric substance in beaker, hold over night, to filter and with the abundant washing copolymer of ethanol, vacuum-drying is to constant weight at 50 DEG C, weigh polymer quality, calculating polymerization catalyst activity is 1.4 × 10
6gpolymer/molTih, Mw are 12054g/ (gmol
-1), PD=Mw/Mn is 3.13.From
13cNMR characterizes and learns (referring to Figure 11), and the polymkeric substance obtained does not have branched structure.
Comparative example 3
Present embodiments provide the obtained complex compound 6 of comparative example 1 as catalyzer, the application in homogeneous catalysis ethene and 1-hervene copolymer close.
Homogeneous catalysis ethene and 1-hervene copolymer close and comprise the following steps:
100mL autoclave ethylene gas with magnetic stir bar, airway is replaced 3 times; under nitrogen protection; add toluene, 1-hexene 10mL, promotor MAO2.5mL (1.60M) [Al/M=1000] successively, 2.0 μm of ol complex compounds 6, control cumulative volume is 100mL; pass into ethylene gas; at 50 DEG C, start polyreaction, maintain ethylene pressure 0.3MPa, stirring reaction 30min; close gas cylinder, by the acidic alcohol termination reaction of 10%.Polymkeric substance is transferred in beaker, hold over night, to filter and with the abundant washing copolymer of ethanol, vacuum-drying is to constant weight at 50 DEG C, weigh polymer quality, calculate polymerization activity 2.2 × 10
6gpolymer/molMh, Mw are 16453g/ (gmol
-1), PD=Mw/Mn is 3.13.From
13cNMR characterizes and learns (referring to Figure 12), and in the polymkeric substance obtained, 1-ahexene content is 3.5mol%.
The Catalytic data of complex compound 1-6 above-described embodiment and comparative example obtained carries out list analysis, and concrete outcome is 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.
Table 1 complex compound/MAO catalyzed ethylene polymerization result
| Complex compound | Act.g polymer/mol Ti·h | Mw g/(g·mol -1) | PD＝Mw/Mn |
| 1 | 2.3×10 6 | 16438 | 5.34 |
| 2 | 2.5×10 6 | 19455 | 6.26 |
| 3 | 5.7×10 6 | 16454 | 4.93 |
| 4 | 1.8×10 6 | 17423 | 5.24 |
| 5 | 5.6×10 6 | 18634 | 4.83 |
| 6 | 1.4×10 6 | 12054 | 3.13 |
Table 2 complex compound/MAO catalyzed ethylene/1-hervene copolymer polymerization result
| Complex compound | Act.g polymer/mol Ti·h | Mw g/(g·mol -1) | PD＝Mw/Mn |
| 1 | 1.1×10 6 | 24359 | 5.24 |
| 2 | 2.7×10 6 | 25424 | 6.16 |
| 3 | 1.0×10 6 | 23869 | 5.43 |
| 4 | 2.1×10 6 | 28742 | 6.24 |
| 5 | 6.4×10 6 | 19452 | 4.86 |
| 6 | 2.2×10 6 | 16453 | 3.13 |
As can be seen from table 1, table 2, the complex compound 1-5 catalyzed ethylene using method provided by the invention to prepare, ethene/1-hexene resulting polymers molecular weight distribution is wider than known monokaryon catalyzer (complex compound 6), there is the molecular weight distribution of regulation and control polymkeric substance, produce the feature of wide distribution polyolefin.
Claims (10)
1. limit a configuration dinuclear metallocene compounds, its structure is such as formula shown in I:
Wherein: R
1be selected from the one in hydrogen, methyl and ethyl;
R
2be selected from the one in hydrogen, methyl and the tertiary butyl;
R
3be selected from the one in ethyl, allyl group, the tertiary butyl, cyclohexyl and phenyl;
R
4for C
2-C
5saturated or containing double bond straight chain hydrocarbon or branched-chain hydrocarbon;
M=Ti or Zr;
X=Cl or Me.
2. restriction configuration dinuclear metallocene compounds according to claim 1, it comprises following compound:
[(tBuNTiCl
2)(η
5-C
5H
4)C(H)]
2[(CH
2)
3]、
[(EtNZrCl
2)(η
5-C
5H
4)C(H)]
2[(CH
2)
2]、
[(tBuNTiCl
2)(η
5-C
5H
4)C(CH
3)]
2[(CH
2)
4]、
[(C
6H
5NZrCl
2)(η
5-C
5H
4)C(CH
3)]
2[(CH
2)
3]、
[(tBuNZrCl
2)(η
5-C
5H
4)C(H)]
2[(CH
2)
3]、
[(tBuNTiCl
2)(η
5-C
5H
4)C(CH
3)]
2[(CH
2)
3]、
[(tBuNZrCl
2)(η
5-C
5H
4)C(CH
3)]
2[(CH
2)
3]、
[(tBuNTiCl
2)(η
5-MeC
5H
3)C(H)]
2[(CH
2)
3]、
[(tBuNZrCl
2)(η
5-MeC
5H
3)C(H)]
2[(CH
2)
3]、
[(Allyl-NTiCl
2)(η
5-C
5H
4)C(H)]
2[(CH
2)
2]、
[(tBuNTiMe
2)(η
5-C
5H
4)C(H)]
2[(CH
2)
3]、
[(Allyl-NZrCl
2)(η
5-C
5H
4)C(H)]
2[(CH
2)
2]、
[(tBuNZrCl
2)(η
5-C
5H
4)C(H)]
2[CH＝CHC(CH
3)]、
[(tBuNTiCl
2)(η
5-C
5H
4)C(CH
3)]
2[CH＝CHC(CH
3)]、
[(tBuNZrCl
2) (η
5-C
5h
4) C (H)]
2[C (CH
3)=CHC (CH
3)
2] or
[(tBuNTiCl
2)(η
5-C
5H
4)C(CH
3)]
2[C(CH
3)＝CHC(CH
3)
2]。
3. a preparation method for the restriction configuration dinuclear metallocene compounds described in claim 1 or 2, wherein, the method comprises the following steps:
(1) dicarbonyl compound and cyclopentadiene is made to react, obtained bridging two fulvene;
(2) make bridging two fulvene and amine lithium react, two lithium salts of obtained ligand L, the structure of described ligand L is such as formula shown in II:
(3) make two lithium salts of ligand L and n-Butyl Lithium be obtained by reacting four lithium salts, then with MCl
42THF, MCl
42Me
2s or reaction, obtained restriction configuration dinuclear metallocene compounds;
Described MCl
4be selected from TiCl
4and ZrCl
4in one.
4. preparation method according to claim 3, wherein, in step (1), uses organic alkali catalyst during cyclopentadiene and dicarbonyl compound react;
In amount of substance, the usage quantity of three kinds of materials meets the following conditions:
Cyclopentadiene: dicarbonyl compound=2.0:1-2.2:1;
Organic bases: dicarbonyl compound=0.05:1-0.1:1;
Preferably, described dicarbonyl compound comprise suceinic aldehyde, glutaraldehyde, hexanedial, heptan dialdehyde, 2,5-hexanediones, 2,6-heptadione or 2,7-acetyl caproyl;
Further preferably, described organic bases comprises methylamine, dimethylamine, ethamine, diethylamine, triethylamine or Pyrrolidine.
5. preparation method according to claim 4, wherein, in step (1), temperature of reaction is-10 DEG C to 30 DEG C, and the reaction times is 1.0-5.0 hour.
6. preparation method according to claim 5, wherein, step (1) comprising:
Under argon shield, dicarbonyl compound, catalysts and solvents are added in reactor, under-10 DEG C to 30 DEG C conditions, add cyclopentadiene, add rear continuation reaction 1.0-5.0 hour, after reaction terminates, obtain described bridging two fulvene through aftertreatment; Described solvent is preferably methyl alcohol or ethanol;
Preferably, described aftertreatment comprises the following steps: except desolventizing after reaction terminates, aqueous phase extracted with diethyl ether, underpressure distillation after organic phase drying, obtains bridging two fulvene.
7. preparation method according to claim 3, wherein, described step (2) comprising:
With ether or tetrahydrofuran (THF) for solvent, under-78 DEG C to 30 DEG C conditions, by the tetrahydrofuran (THF) of bridging two fulvene instillation amido lithium obtained for step (1) or diethyl ether solution, described amido lithium is 2.0:1-2.2:1 with the ratio of the amount of substance of described bridging two fulvene, 20 DEG C are warmed up to reflux temperature after dropwising, reaction 3-6 hour, removal of solvent under reduced pressure obtains solid matter, and above-mentioned solid matter obtains two lithium salts of ligand L through aftertreatment;
Preferably, described amido lithium comprises methylamine lithium, ethylamine lithium, allyl amine lithium, TERTIARY BUTYL AMINE lithium, cyclo-hexylamine lithium or aniline lithium;
Further preferably, by described solid matter hydrolysis, separatory, the organic phase drying after separatory concentrates the two lithium salts obtaining ligand L; Or washed by described solid matter alkane, then the dry two lithium salts obtaining ligand L, described alkane is preferably Skellysolve A or normal hexane.
8. preparation method according to claim 3, wherein, described step (3) comprising:
Two lithium salts of ligand L step (2) obtained are dissolved in tetrahydrofuran (THF), under-78 DEG C to 30 DEG C conditions, the hexane solution of instillation butyllithium, butyllithium is 4.0:1-4.8:1 with the ratio of the amount of substance of the two lithium salts of ligand L, 20 DEG C are warmed up to reflux temperature after dropwising, reaction 3-6 hour, except desolventizing obtains solid, the solid obtained obtains four lithium salts of ligand L through aftertreatment;
By four lithium salts of above-mentioned ligand L at-80 DEG C to 30 DEG C condition low suspensions in ether or tetrahydrofuran solution, add MCl
4, be warmed up to 0 DEG C to reflux temperature, reaction 3-10 hour, except desolventizing obtains solid, the solid obtained obtains restriction configuration binuclear metallocene catalyzer through aftertreatment;
Preferably, the step of described aftertreatment comprises: by solid matter hydrolysis, separatory, and the organic phase drying after separatory concentrates four lithium salts or restriction configuration binuclear metallocene catalyzer that obtain ligand L; Or washed by described solid matter alkane, then dry four lithium salts or the restriction configuration binuclear metallocene catalyzer obtaining ligand L, described alkane is preferably Skellysolve A or normal hexane.
9. the restriction configuration dinuclear metallocene compounds described in claim 1 or 2 in olefinic polyreaction and copolyreaction as the application of catalyzer.
10. application according to claim 9, wherein, described restriction configuration dinuclear metallocene compounds is as Primary Catalysts, and methylaluminoxane is as promotor, and Primary Catalysts is 1:500-2000 with the amount of substance ratio of promotor.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108840887A (en) * | 2018-04-28 | 2018-11-20 | 中国石油天然气股份有限公司 | A kind of sPP bridged binuclear metallocene compound and the preparation method and application thereof |
| CN112552429A (en) * | 2019-09-25 | 2021-03-26 | 中国石油天然气股份有限公司 | Supported metallocene catalyst and preparation method and application thereof |
| CN114195920A (en) * | 2021-11-29 | 2022-03-18 | 青岛科技大学 | Synthesis of improved metallocene catalyst, synthesis equipment and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1270596A (en) * | 1997-09-15 | 2000-10-18 | 陶氏化学公司 | Bimetallic complexes and polymerization catalysts therefrom |
| US6235917B1 (en) * | 1998-08-28 | 2001-05-22 | The Dow Chemical Company | Dinuclear complexes and polymerization catalysts therefrom |
| US6284698B1 (en) * | 1997-09-15 | 2001-09-04 | The Dow Chemical Company | Highly activated bimetallic complexes and polymerization process |
| CN104513280A (en) * | 2014-12-25 | 2015-04-15 | 中国石油天然气股份有限公司 | Bridged dinuclear metallocene compound for sPP as well as preparation method and application thereof |
-
2015
- 2015-10-29 CN CN201510717552.9A patent/CN105273010B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1270596A (en) * | 1997-09-15 | 2000-10-18 | 陶氏化学公司 | Bimetallic complexes and polymerization catalysts therefrom |
| US6284698B1 (en) * | 1997-09-15 | 2001-09-04 | The Dow Chemical Company | Highly activated bimetallic complexes and polymerization process |
| US6235917B1 (en) * | 1998-08-28 | 2001-05-22 | The Dow Chemical Company | Dinuclear complexes and polymerization catalysts therefrom |
| CN104513280A (en) * | 2014-12-25 | 2015-04-15 | 中国石油天然气股份有限公司 | Bridged dinuclear metallocene compound for sPP as well as preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| CRISTINA PANIAGUA等，: "Reactions of [Ti(η5-C5Me4SiMe2Cl)Cl3] with Diamines, a Suitable Approach to Prepare Mono- and Dinuclear Cyclopentadienylsilyl-amido Titanium Complexes with Constrained and Unstrained Structures", 《ORGANOMETALLICS》 * |
| MIN HYUNG LEE等，: "A biphenylene-bridged dinuclear constrained geometry titanium complex for ethylene and ethylene/1-octene polymerizations", 《JOURNAL OF ORGANOMETALLIC CHEMISTRY》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108840887A (en) * | 2018-04-28 | 2018-11-20 | 中国石油天然气股份有限公司 | A kind of sPP bridged binuclear metallocene compound and the preparation method and application thereof |
| CN108840887B (en) * | 2018-04-28 | 2021-03-30 | 中国石油天然气股份有限公司 | Bridged dinuclear metallocene compound for sPP (sPP), and preparation method and application thereof |
| CN112552429A (en) * | 2019-09-25 | 2021-03-26 | 中国石油天然气股份有限公司 | Supported metallocene catalyst and preparation method and application thereof |
| CN112552429B (en) * | 2019-09-25 | 2022-08-05 | 中国石油天然气股份有限公司 | Supported metallocene catalyst and preparation method and application thereof |
| CN114195920A (en) * | 2021-11-29 | 2022-03-18 | 青岛科技大学 | Synthesis of improved metallocene catalyst, synthesis equipment and application thereof |
| CN114195920B (en) * | 2021-11-29 | 2023-07-18 | 青岛科技大学 | Synthesis of improved metallocene catalyst, synthesis equipment and application thereof |
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