CN102260284A - Novel ethylene-bridged indenyl fluorene zirconium compound, as well as preparation method and application of compound in high-selectivity catalysis of propylene dimerization - Google Patents
Novel ethylene-bridged indenyl fluorene zirconium compound, as well as preparation method and application of compound in high-selectivity catalysis of propylene dimerization Download PDFInfo
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Abstract
The invention discloses an ethylene-bridged indenyl fluorene zirconium compound, as well as a preparation method and an application of the compound in polymerization and oligomerization of alpha-olefin. In the preparation method, the ethylene-bridged indenyl fluorene zirconium compound can be prepared by reacting an ethylene-bridged indenyl fluorene ligand compound with an alkyl alkali metal in an organic medium and then adding ZrCl4. The ethylene-bridged indenyl fluorene zirconium compound disclosed by the invention has the following characteristics: R1 and R2 separately represent C1-C10 straight-chain or branched-chain alkyl, and R1 and R2 can be connected to form a cyclic structure; and R3 represents hydrogen, C1-C12 straight-chain or branched-chain or cyclic-structured alkyl or alkenyl. The ethylene-bridged indenyl fluorene zirconium compound disclosed by the invention is an efficient catalyst, and is used for catalyzing propylene oligomerization to obtain 2-methyl-1-pentene at high selectivity. The general structural formula of the ethylene-bridged indenyl fluorene zirconium compound is shown in the specification.
Description
Technical field
The present invention relates to class ethidene bridged linkage indene fluorene zirconium compound and preparation method thereof, relate in particular to the application of this compounds in the catalyzing propone oligomerisation.
Background technology
At the beginning of the fifties in last century, Ziegler-Natta catalyst (J.Am.Chem.Soc., 1957,79,2975) is applied to the success of olefinic polymerization, makes polymer industry obtain fast development.The beginning of the eighties, Sinn (Angew.Chem.Int.Ed.Engl., 1980,92,396) and Kaminsky (Macromol.Chem., Rapid Commun., 1983,4,417) but etc. the people found the homogeneous catalytic olefin polymerization system highly active catalytic olefinic polymerization that metallocene complex and MAO form.Compare with traditional heterogeneous Ziegler-Natta catalyst, the microcosmic three-dimensional arrangement of the electronegativity at homogeneous phase metallocene catalyst reactive metal center and space environment remarkably influenced gained polyolefine macromolecular chain, subtle change on the metallocene complex ligand structure, all might on the microtexture of polymkeric substance, be embodied, produce thus many Ziegler-Natta heterogeneous catalysts the polyolefin structure that can't obtain, as random, syndiotactic polypropylene, hemiisotactic polypropylene, syndiotactic polystyrenes etc. show excellent controllability.
Middle nineteen nineties in last century, Rieger (Organometallics, 1994,13,647) and Chien (J.Organomet.Chem., 1995,497,1) etc. seminar has reported a series of indenes fluorenes zirconium metal complexs that contain different bridge foundation: X (Ind) is ZrCl (Flu)
2(X=CH
2CH
2, Me
2Si, PhCHCH
2, etc.), be used for the catalyzing propone polymerization, have advantages of high catalytic activity and medium isotactic selectivity.(J.Mol.Catal.A:Chem. such as Alt seminar (EP 0853086) and Siedle, 2003,191,167) also this class bridging type indenes fluorenes metal complex some researchs have been carried out, introduce various alkyl substituents in indenes 3-position, be used for the catalyzing propone polymerization, to obtain having the polypropylene of higher isotactic regularity.3M company (WO 9920664) has reported the indenes fluorenes zirconium metal complex that the alkyl of various ethidene bridged linkages replaces, and its propylene catalytic activity is studied, and has obtained the polypropylene of higher molecular weight.
Use metallocene complex not only can obtain the high-molecular weight polyolefine by catalysis in olefine polymerization, also can the oligomerisation of catalysis alpha-olefin, obtain more high-grade alkene, propylene dimerization is exactly wherein a kind of.
Propylene dimerization can obtain various six carbon olefin products, has the purposes as the aspects such as precursor of sanitising agent, artificial oil and plasticizer, and is widely studied.Main employing an alkali metal salt is a catalyzer in the industrial production at present, and (US 4554790 as Phillip Perolenm Company; US.4988658) Bao Dao salt of wormwood catalyst system.SUMITOMO CHEMICAL company adopts nickel naphthenate system catalyzing propone dimerization, obtains 2, and the selectivity of 3-neohexene is 80% (Bull Chem.Soc.Jpn., 1993,66,3069), but its activity is not high; The selectivity that the Dalian Chemistry and Physics Institute adopts (beta-ketimine) nickel or the oligomerisation of cobalt complex catalyzing propone to obtain six carbon olefins is 70-90%, and the content of methylpentene is 80% (CN 1449867) in the dimerisation products; Eisen has reported that bidentate imide nickel complex/MMAO catalyst system catalyzing propone oligomerisation shows advantages of high catalytic activity, and product is the mixture (Organometallics, 2005,24,2645) of various hexenes; The vanadium catalyst of Alt report can show 4-methyl 1-amylene in the catalyzing propone dimerization and surpass 90% highly selective.(J.Mol.Catal.A：Chem.，2010，322，45-49)。
Adopt the report of metallocene complex catalyzing propone dimerization more limited.Dow Chemical is with the two luxuriant uranium compound catalyzing propone dimerization that replace, and the selectivity that obtains 4-methyl isophthalic acid amylene can be up to 98% (US 4855523), but this type of catalyzer exists and costs an arm and a leg and problem that the life-span is short.Kaminsky etc. (Macromol.Symp.1995,89,203) utilize bridging tetrahydroindenyl zirconium compound for catalysis propylene dimerization, obtain 2-methyl 1-amylene, and selectivity reaches 99%, but catalytic activity is very low.Mitsui KCC is with two metallocene complex catalyzing propone dimerization (WO 2006085531) of non-bridging type, and products therefrom complicated component, primary product are 4-methyl-1-pentene, and its high-content is 61.6%.This seminar (CN 201010105907) discloses the C that a class indenes 3-position has big steric hindrance aryl to replace
1-symmetrical bridging type indenes fluorenes zirconium complex, its catalyzing propone oligomerisation, highly selective has obtained 2-methyl 1-amylene.
Bridging type indenes fluorenes zirconium complex generally is used for catalyzed ethylene and propylene polymerization, except that the report of this seminar (CN201010105907), as yet not relevant for the report of catalyzing propone dimerization.In addition, there is the C that big steric hindrance aryl replaces the indenes ring 3-position of previous report
1-symmetrical bridging type indenes fluorenes zirconium complex is because of being subjected to the influence of strong coordination of aryl and steric hindrance, and catalytic activity is still lower.
Along with science and technology development, that people wish is can the development research activity higher, cost is lower, can produce the metallocene complex catalyzer with special purpose polymkeric substance, to satisfy industrial demand.
Summary of the invention
One of the object of the invention is to disclose a class ethylene bridge biindyl fluorenes Zr metal compound.
Two of the object of the invention is to disclose the preparation method of such ethylene bridge biindyl fluorenes Zr metal compound.
Three of the object of the invention is to disclose such ethylene bridge biindyl fluorenes Zr metal compound as the application of catalyzer in propylene dimerization.
Technical conceive of the present invention:
This seminar has reported that indenes ring 3-position has the bridging type indenes fluorenes zirconium complex that big steric hindrance aryl replaces, and in the presence of alkylaluminoxane, has realized the polymerization and the oligomerisation of alkene.But be subjected to the influence of the strong coordination of aryl, catalytic activity is lower.For this reason, the present invention introduces the various substituting groups of non-aryl in the 3-position of part indenes ring, wishes to improve the activity of catalyzing propone dimerization by regulating electronics and steric effect when keeping highly selective.
Ethidene bridged linkage indene fluorene zirconium compound provided by the invention has following general formula:
In the formula (I), R
1, R
2Represent C respectively
1～C
10Straight chain, branched-chain alkyl, R
1And R
2The formation ring texture also can link to each other; R
3Represent hydrogen, C
1～C
12Alkyl, the thiazolinyl of straight chain, side chain or ring texture.
R
1, R
2Be respectively C
1～C
6The alkyl of straight chain, branched structure, R
1And R
2Also can be connected to ring and constitute C
4～C
8Cyclic alkyl; R
3Represent hydrogen, C
1～C
6The alkyl of straight chain, side chain, ring texture, thiazolinyl.
More feature is R
1, R
2Be preferably methyl, R
1, R
2Link to each other and constitute cyclohexyl; R
3Be preferably hydrogen, normal-butyl, cyclohexyl, cyclohexenyl.
The preparation method of ethidene bridged linkage indene fluorene zirconium compound of the present invention, as follows:
Comprise the steps:
(1) ethylene bridge biindyl fluorenes ligand compound and the alkali alkyl compound shown in the formula (II) reacted in organic medium, generate two an alkali metal salts of ethylene bridge biindyl fluorenes part.
Described alkali alkyl compound is selected from C
1～C
4Lithium alkylide, more preferably butyllithium; Described organic medium is selected from one or more in tetrahydrofuran (THF), ether, toluene, benzene, chloroform, methylene dichloride and the sherwood oil.
Temperature of reaction is-78～25 ℃, and the reaction times is 2～24 hours, and the ethylene bridge biindyl fluorenes ligand compound shown in the formula (II) and the molar ratio of alkali alkyl compound are: 1: 2～2.5.
(2) with two an alkali metal salts of the ethylene bridge biindyl fluorenes part of step (1) in organic medium with ZrCl
4Reaction, temperature of reaction is-78～25 ℃, the reaction times is 2～24 hours, collects target compound then from reaction product; An alkali metal salt and the ZrCl of ethylene bridge biindyl fluorenes class part
4Molar ratio be: 1: 1～1.2.
Part complex structure of the present invention is exemplified below:
Ethidene bridged linkage indene fluorene zirconium compound of the present invention is a kind of catalyzer of propylene dimerization efficiently, has advantages of high catalytic activity, and highly selective obtains the 2-Methyl-1-pentene.
With ethidene bridged linkage indene fluorene zirconium compound of the present invention is Primary Catalysts, is promotor with the alkylaluminoxane, and preferable methyl aikyiaiurnirsoxan beta (MAO) makes propylene at 0～110 ℃, polymerization under 0.1～1.5MPa condition.Promotor is 500～15000: 1 with the metal molar ratio of Primary Catalysts during polymerization.Change reaction conditions, the dimerization activity of catalyzer has change in various degree.Optimal conditions is: Al/Zr is 4000: 1; Preferred 50～70 ℃ of polymerization temperature; Catalyst concn is 0.5 * 10
-4Mol/L～3 * 10
-4Mol/L; Polymerization time is 15～120min, is preferably 30min.
Catalyzer raw material provided by the invention is easy to get, and is easy to prepare, and stable in properties has advantages of high catalytic activity simultaneously, and highly selective obtains propylene dimerization and obtains the 2-Methyl-1-pentene.Can satisfy the needs of industrial sector, have a wide range of applications.
Further specify the present invention below by example, but the invention is not restricted to this.
Embodiment
Embodiment 1
Synthetic zirconium complex C1
(1) the synthetic indenes I1 that replaces
In the 100mL normal hexane, add the 1.95g metallic lithium, add the 15g chlorocyclohexane again, stir 2h, add benzo fulvene 19g, after continuing to stir 2h, boil off solvent, underpressure distillation, 0.1mmHg/98～100 ℃, product 10.1g, productive rate 33.3%.
1H?NMR(400MHz，298K，CDCl
3)：δ7.65(d，J＝7.5Hz，1H，Ar-H)，7.46(d，J＝7.4Hz，1H，Ar-H)，7.26(t，J＝7.5Hz，1H，Ar-H)，7.17(td，J＝7.5，0.8Hz，1H，Ar-H)，6.18(t，J＝2.1Hz，1H，2-Ind-H)，3.30(d，J＝2.1Hz，2H，3-Ind-H)，1.98(m，1H，CHC(CH
3)
2)，1.78-1.57(m，5H，Cy-H)，1.28(s，6H，C(CH
3)
2)，1.23-0.93(m，5H，Cy-H).
(2) the synthetic ligands compound L 1
2g is replaced indenes I1 add in the reaction flask, behind the adding 30mL sherwood oil, drip 3.5mL (2.4mol/L) n-butyllithium solution, drip and finish, stir 2h, get the canescence powdery solid, add the 30mL ether dissolution.Drip the mixing solutions of 1.9g 9-(2-bromo-ethyl)-fluorenes and 20mL ether, add 40mL saturated aqueous ammonium chloride stopped reaction behind the stirring 4h, use the 100mL extracted with diethyl ether again, the yellow liquid anhydrous magnesium sulfate drying of gained.Filtration, recrystallization get white solid L11.0g, productive rate 28.5%.
1H?NMR(400MHz，298K，CDCl
3)：δ7.75(d，J＝7.2Hz，2H，Ar-H)，7.74(d，J＝7.2Hz，2H，Ar-H)，7.56(d，J＝7.6Hz，1H，Ar-H)，7.49(d，J＝7.2Hz，1H，Ar-H)，7.44-7.26(m，5H，Ar-H)，7.24-7.18(m，2H，Ar-H)，7.12(t，J＝7.4Hz，1H，Ar-H)，6.06(d，J＝1.6Hz，1H，2-Ind-H)，3.95(t，J＝5.4Hz，1H，9-Flu-H)，3.25(t，J＝5.4Hz，1H，1-Ind-H)，2.13-2.00(m，1H，Ind-CH
2CH
2-Flu)，2.00-1.80(m，1H，Ind-CH
2CH
2-Flu)，1.78-1.58(m，5H，Cy-H)，1.40-1.30(m，1H，Ind-CH
2CH
2-Flu)，1.24(s，6H，C(CH
3)
2)，1.20-0.82(m，6H，Cy-H).
(3) synthetic complex compound C1
In 0.9g ligand L 1 adding reaction flask, add the 30mL anhydrous diethyl ether, drip 1.75mL (2.4mol/L) n-butyllithium solution, drip and finish, add 0.49g ZrCl behind the stirring 2h
4, continue to stir 4h.With the methylene dichloride dissolving, recrystallization is separated out red crystals C10.5g, productive rate 40.0%.
1H?NMR(400MHz，298K，CDCl
3)：δ8.01(d，J＝8.5Hz，1H，Ar-H)，7.90(d，J＝8.4Hz，1H，Ar-H)，7.83(d，J＝8.5Hz，1H，Ar-H)，7.77(d，J＝8.4Hz，1H，Ar-H)，7.66-7.58(m，2H，Ar-H)，7.54(d，J＝8.6Hz，1H，Ar-H)，7.40(t，J＝7.6Hz，1H，Ar-H)，7.29(t，J＝6.8Hz，1H，Ar-H)，7.17-7.01(m，3H)，5.92(s，1H，2-Ind-H)，4.60(m，1H，IndCH
2CH
2Flu)，4.08(m，1H，IndCH
2CH
2Flu)，4.03-3.92(m，2H，IndCH
2CH
2Flu)，1.71(t，J＝12Hz，Cy-H)，1.54(s，3H，C(CH
3)
2)，1.51-1.29(m，3H，Cy-H)，1.11(s，3H，C(CH
3)
2)，1.09-1.02(m，1H，Cy-H)，1.00-0.80(m，2H，Cy-H)，0.72(ddt，J＝25.6，12.8，3.6Hz)1H，Cy-H)，0.59(ddd，J＝24.7，12.3，3.2Hz，1H，Cy-H)，0.3-0.19(m，1H，Cy-H).
Embodiment 2
Synthetic zirconium complex C2
(1) the synthetic indenes I2 that replaces
In the 100mL normal hexane, add the 1.2g metallic lithium, drip 8g chloro tetrahydrobenzene again, stir 2h, add benzo fulvene 11g, after continuing to stir 2h, boil off solvent, underpressure distillation, 0.1mmHg/94～96 ℃, product 6g, productive rate 40.2%.
1H?NMR(400MHz，298K，CDCl
3)：δ7.52(d，1H，J＝7.6Hz，Ar-H)，7.42(d，1H，J＝7.3Hz，Ar-H)，7.20(t，1H，J＝7.6Hz，Ar-H)，7.14(t，1H，J＝7.3Hz，Ar-H)，6.26(s，1H，2-Ind-CH)，5.73(d，9.5Hz，1H，C＝CH)，3.30(s，2H，3-Ind-CH
2)，2.16-2.07(m，2H，Hex-CH)，1.84-1.74(m，2H，Hex-CH)，1.53-1.45(m，4H，Hex-CH)，1.41(s，6H，C(CH
3)
2).
(2) the synthetic ligands compound L 2
0.94g is replaced indenes I2 add in the reaction flask, behind the adding 30mL sherwood oil, drip 1.7mL (2.4mol/L) n-butyllithium solution, drip and finish, stir 2h, get the canescence powdery solid, add the 30mL ether dissolution.Drip the mixing solutions of 1.2g 9-(2-bromo-ethyl)-fluorenes and 20mL ether, add 40mL saturated aqueous ammonium chloride stopped reaction behind the stirring 4h, use the 100mL extracted with diethyl ether again, the yellow liquid anhydrous magnesium sulfate drying of gained.Filtration, recrystallization get white solid L21.1g, productive rate 89.3%.
1H?NMR(400MHz，298K，CDCl
3)：δ7.74(dd，J＝7.3，3.0Hz，2H，Ar-H)，7.49(d，J＝7.2Hz，1H，Ar-H)，7.44-7.09(m，9H，Ar-H)，6.13(d，J＝1.9Hz，1H，2-Ind-CH)，5.72(t，J＝3.7Hz，1H，Hex-CH)，3.95(t，J＝5.6Hz，1H，9-Flu-CH)，3.28(td，J＝6.1，1.9Hz，1H，1-Ind-CH)，2.14-2.06(m，2H，Hex-CH
2)，2.06-2.00(m，1H，CH
2CH
2)，1.94-1.82(m，1H，CH
2CH
2)，1.80-1.74(m，2H，Hex-CH
2)，1.76-1.64(m，1H，CH
2CH
2)，1.56-1.45(m，4H，Hex-CH
2)，1.44-1.32(m，1H，CH
2CH
2)，1.39(s，3H，CH
3)，1.37(s，3H，CH
3).
(3) synthetic complex compound C2
In 1.2g ligand L 2 adding reaction flasks, add the 30mL anhydrous diethyl ether, drip 2.3mL (2.4mol/L) n-butyllithium solution, drip and finish, add 0.65g ZrCl behind the stirring 2h
4, continue to stir 4h.With the methylene dichloride dissolving, recrystallization is separated out red powder C20.25g, productive rate 15.1%.
1H?NMR(400MHz，298K，CDCl
3)：δ8.15-8.09(m，1H，Ar-H)，7.91(d，J＝8.4Hz，1H，Ar-H)，7.87(d，J＝8.5Hz，1H，Ar-H)，7.78(d，J＝8.4Hz，1H，Ar-H)，7.66(t，J＝7.6Hz，1H，Ar-H)，7.53(d，J＝8.6Hz，1H，Ar-H)，7.50-7.40(m，2H，Ar-H)，7.30(t，J＝7.6Hz，1H，Ar-H)，7.14-7.05(m，3H，Ar-H)，6.02(s，1H，2-Ind-H)，5.51(s，1H，CH＝C)，4.78-4.65(m，1H，Ind-CH
2CH
2-Flu)，4.26-4.10(m，1H，Ind-CH
2CH
2-Flu)，4.03-3.90(m，2H，Ind-CH
2CH
2-Flu)，2.04-1.90(m，1H，Cyclohexene-H)，1.66(s，3H，C(CH
3)
2)，1.63-1.58(m，1H，Cyclohexene-H)，1.43-1.21(m，3H，Cyclohexene-H)，1.34(s，3H，C(CH
3)
2)，1.17-1.05(m，1H，Cyclohexene-H)，0.76-0.64(m，1H，Cyclohexene-H).
Embodiment 3
Synthetic zirconium complex C3
(1) the synthetic indenes I3 that replaces
Add 24mL n-Butyl Lithium (2.4mol/L) in the 100mL normal hexane, drip benzo fulvene 11g again, after continuing to stir 2h, boil off solvent, chromatographic column is separated, and eluent is a sherwood oil, gets product 6g, productive rate 50.2%.
1H?NMR(400MHz，298K，CDCl
3)：δ7.64(d，J＝7.5Hz，1H，Ar-H)，7.47(d，J＝7.4Hz，1H，Ar-H)，7.27(t，J＝7.5Hz，1H，Ar-H)，7.18(td，J＝7.4，0.8Hz，1H，Ar-H)，6.19(t，J＝2.1Hz，1H，2-Ind-CH)，3.31(d，J＝2.1Hz，2H，3-Ind-CH
2)，1.81-1.74(m，2H，-CH
2CH
2CH
2CH
3)，1.34(s，6H，C(CH
3)
2)，1.27-1.18(m，2H，-CH
2CH
2CH
2CH
3)，1.17-1.06(m，2H，-CH
2CH
2CH
2CH
3)，0.83(t，J＝7.3Hz，3H，-CH
2CH
2CH
2CH
3).
(2) the synthetic ligands compound L 3
1.5g is replaced indenes I3 add in the reaction flask, behind the adding 30mL sherwood oil, drip 3.0mL (2.4mol/L) n-butyllithium solution, drip and finish, stir 2h, get the canescence powdery solid, add the 30mL ether dissolution.Drip the mixing solutions of 1.9g 9-(2-bromo-ethyl)-fluorenes and 20mL ether, add 40mL saturated aqueous ammonium chloride stopped reaction behind the stirring 4h, use the 100mL extracted with diethyl ether again, the yellow liquid anhydrous magnesium sulfate drying of gained.Filtration, recrystallization get white solid L31.6g, productive rate 55.9%.
1H?NMR(400MHz，298K，CDCl
3)：δ7.75(dd，J＝7.3，3.1Hz，2H，Ar-H)，7.55(d，J＝7.6Hz，1H，Ar-H)，7.50(d，J＝7.3Hz，1H，Ar-H)，7.43-7.27(m，5H，Ar-H)，7.25-7.19(m，1H，Ar-H)，7.13(t，J＝7.0Hz，1H，Ar-H)，6.06(d，J＝2.0Hz，1H，2-Ind-H)，3.95(t，J＝5.6Hz，1H，9-Flu-H)，3.26(td，J＝6.4，2.0Hz，1H，1-Ind-H)，2.15-2.05(m，1H，Ind-CH
2CH
2-Flu)，1.95-1.83(m，1H，Ind-CH
2CH
2-Flu)，1.82-1.63(m，3H，Ind-CH
2CH
2-Flu，-CH
2CH
2CH
2CH
3)，1.42-1.02(m，6H，-CH
2CH
2CH
2CH
3)，1.31(s，3H，C(CH
3)
2)，1.30(s，3H，C(CH
3)
2)，0.8(t，J＝7.2Hz，3H，-CH
2CH
2CH
2CH
3).
(3) synthetic complex compound C3
In 1.6g ligand L 3 adding reaction flasks, add the 30mL anhydrous diethyl ether, drip 3.3mL (2.4mol/L) n-butyllithium solution, drip and finish, add 0.93g ZrCl behind the stirring 2h
4, continue to stir 4h.With the methylene dichloride dissolving, recrystallization is separated out red powder C30.5g, productive rate 22.1%.
1H?NMR(400MHz，298K，CDCl
3)：δ8.04(d，J＝8.8Hz，1H，Ar-H)，7.90(d，J＝8.4Hz，Ar-H)，7.83(d，J＝8.8Hz，1H，Ar-H)，7.77(d，J＝8.4Hz，1H，Ar-H)，7.66-6.57(m，2H，Ar-H)，7.53(d，J＝8.8Hz，1H，Ar-H)，7.40(t，J＝7.6Hz，1H，Ar-H)，7.29(t，J＝7.6Hz，1H，Ar-H)，7.15-7.04(m，3H，Ar-H)，6.21(s，1H，2-Ind-CH)，4.70-4.55(m，1H，Ind-CH
2CH
2-Flu)，4.18-4.05(m，1H，Ind-CH
2CH
2-Flu)，4.03-3.93(m，2H，Ind-CH
2CH
2-Flu)，1.63(td，J＝12.7，4.5Hz，1H，-CH
2CH
2CH
2CH
3)，1.45(s，3H，C(CH
3)
2)，1.38(td，J＝13.1，3.5Hz，1H，-CH
2CH
2CH
2CH
3)，1.23(s，3H，C(CH
3)
2，-CH
2CH
2CH
2CH
3)，1.13-0.92(m，3H，-CH
2CH
2CH
2CH
3)，0.68(t，J＝7.0Hz，3H，-CH
2CH
2CH
2CH
3)，0.50-0.36(m，1H，-CH
2CH
2CH
2CH
3).
Embodiment 4
Synthetic zirconium complex C4
(1) the synthetic indenes I4 that replaces
18mL n-Butyl Lithium (2.4mol/L) in the 5g indenes stirs 2h, drips isopropyl bromide 5.3g again, after continuing to stir 2h, underpressure distillation, 5mmHg/78～80 ℃ product 6g, productive rate 88%.
1H?NMR(400MHz，298K，CDCl
3)：δ7.48(d，J＝7.4Hz，1H，Ar-H)，7.43(d，J＝7.5Hz，1H，Ar-H)，7.31(t，J＝7.4Hz，1H，Ar-H)，7.21(td，J＝7.5，0.8Hz，1H，Ar-H)，6.21(d，J＝1.4Hz，1H，2-Ind-CH)，3.33(s，2H，3-Ind-CH
2)，2.97(Hept，J＝6.8，1.4Hz，1H，CH(CH
3)
2)，1.30(d，J＝6.8Hz，6H，CH(CH
3)
2).
(2) the synthetic ligands compound L 4
3g is replaced indenes I4 add in the reaction flask, behind the adding 30mL sherwood oil, drip 7.9mL (2.4mol/L) n-butyllithium solution, drip and finish, stir 2h, get the canescence powdery solid, add the 30mL ether dissolution.Drip the mixing solutions of 4g 9-(2-bromo-ethyl)-fluorenes and 20mL ether, add 40mL saturated aqueous ammonium chloride stopped reaction behind the stirring 4h, use the 100mL extracted with diethyl ether again, the yellow liquid anhydrous magnesium sulfate drying of gained.Filtration, recrystallization get white solid L41.6g, productive rate 24.2%.
1H?NMR(400MHz，298K，CDCl
3)：δ7.82-7.68(m，1H，Ar-H)，7.51(d，J＝7.3Hz，1H，Ar-H)，7.43(d，J＝7.3Hz，1H，Ar-H)，7.40-7.27(m，6H，Ar-H)，7.16(t，J＝7.2Hz，Ar-H)，6.09(s，1H，2-Ind-H)，3.97(t，J＝5.5Hz，1H，9-Flu-H)，3.29(t，J＝6.3Hz，1H，1-Ind-H)，2.89(m，1H，CH(CH
3)
2)，2.18-2.06(m，1H，Ind-CH
2CH
2-Flu)，2.00-1.88(m，1H，Ind-CH
2CH
2-Flu)，1.76-1.64(m，1H，Ind-CH
2CH
2-Flu)，1.45-1.30(m，1H，Ind-CH
2CH
2-Flu)，1.28(d，J＝6.8Hz，1H，CH(CH
3)
2)，1.25(d，J＝6.8Hz，1H，CH(CH
3)
2).
(3) synthetic complex compound C4
In 1.2g ligand L 4 adding reaction flasks, add the 30mL anhydrous diethyl ether, drip 2.9mL (2.4mol/L) n-butyllithium solution, drip and finish, add 0.80g ZrCl behind the stirring 2h
4, continue to stir 4h.With the methylene dichloride dissolving, recrystallization is separated out red powder C40.5g, productive rate 28.7%.
1H?NMR(400MHz，298K，CDCl
3)：δ7.96(d，J＝8.4Hz，1H，Ar-H)，7.90(d，J＝8.4Hz，1H，Ar-H)，7.76(d，J＝8.4Hz，1H，Ar-H)，7.70(d，J＝8.4Hz，1H，Ar-H)，7.50(t，J＝7.2Hz，1H，Ar-H)，7.46-7.27(m，5H)，7.08-6.99(m，2H)，6.32(s，1H，2-Ind-H)，4.32-4.22(m，1H，IndCH
2CH
2Flu)，4.19-4.08(m，1H，IndCH
2CH
2Flu)，4.07-3.99(m，1H，IndCH
2CH
2Flu)，3.75-3.66(m，1H，IndCH
2CH
2Flu)，3.22(Hept，J＝6.8Hz，1H，HC(CH
3)
2)，1.09(d，J＝6.8Hz，3H，HC(CH
3)
2)，0.96(d，J＝6.8Hz，3H，HC(CH
3)
2).
Embodiment 5
Synthetic zirconium complexing C5 thing
(1) the synthetic indenes I5 that replaces
18mL n-Butyl Lithium (2.4mol/L) in the 5g indenes stirs 2h, drips cyclohexyl chloride 5.2g again, after continuing to stir 2h, underpressure distillation, 5mmHg/92～94 ℃ product 3.5g, productive rate 44%.
1H?NMR(400MHz，298K，CDCl
3)：δ7.46(d，1H，J＝7.4Hz，Ar-H)，7.41(d，1H，J＝7.4Hz，Ar-H)，7.29(d，1H，J＝7.4Hz，Ar-H)，7.19(d，1H，J＝7.4Hz，Ar-H)，6.17(t，1H，J＝1.2Hz，2-Ind-CH)，3.31(s，2H，3-Ind-CH
2)，2.58(t，J＝10.6Hz，1H，Cy-H)，2.06(d，2H，J＝11.1Hz，Cy-H)，1.88-1.75(m，3H，Cy-CH)，1.48-1.26(m，5H，Cy-H).
(2) the synthetic ligands Compound I 5
1.95g is replaced indenes I5 add in the reaction flask, behind the adding 30mL sherwood oil, drip 4.5mL (2.4mol/L) n-butyllithium solution, drip and finish, stir 2h, get the canescence powdery solid, add the 30mL ether dissolution.Drip the mixing solutions of 2g 9-(2-bromo-ethyl)-fluorenes and 20mL ether, add 40mL saturated aqueous ammonium chloride stopped reaction behind the stirring 4h, use the 100mL extracted with diethyl ether again, the yellow liquid anhydrous magnesium sulfate drying of gained.Filtration, recrystallization get white solid L51.1g, productive rate 31.2%.
1H?NMR(400MHz，298K，CDCl
3)：δ7.75(d，J＝7.2Hz，2H，Ar-H)，7.74(d，J＝7.2Hz，2H，Ar-H)，7.56(d，J＝7.6Hz，1H，Ar-H)，7.49(d，J＝7.2Hz，1H，Ar-H)，7.44-7.26(m，5H，Ar-H)，7.24-7.18(m，2H，Ar-H)，7.12(t，J＝7.4Hz，1H，Ar-H)，6.06(d，J＝1.6Hz，1H，2-Ind-H)，3.95(t，J＝5.4Hz，1H，9-Flu-H)，3.25(t，J＝5.4Hz，1H，1-Ind-H)，2.13-2.00(m，1H，Ind-CH
2CH
2-Flu)，2.00-1.80(m，1H，Ind-CH
2CH
2-Flu)，1.78-1.58(m，5H，Cy-H)，1.40-1.30(m，1H，Ind-CH
2CH
2-Flu)，1.24(s，6H，C(CH
3)
2)，1.20-0.82(m，6H，Cy-H)
(3) synthetic complex compound C5
In 1.3g ligand L 5 adding reaction flasks, add the 30mL anhydrous diethyl ether, drip 2.8mL (2.4mol/L) n-butyllithium solution, drip and finish, add 0.77g ZrCl behind the stirring 2h
4, continue to stir 4h.With the methylene dichloride dissolving, recrystallization is separated out red powder C50.4g, productive rate 16.7%.
1H?NMR(400MHz，298K，CDCl
3)：δ7.97(d，J＝8.4Hz，1H，Ar-H)，7.90(d，J＝8.4Hz，1H，Ar-H)，7.75(d，J＝8.4Hz，1H，Ar-H)，7.670(d，J＝8.5Hz，1H，Ar-H)，7.51(t，J＝7.6Hz，1H，Ar-H)，7.46-7.41(m，1H，Ar-H)，7.37(dd，J＝15.8，8.3Hz，2H，Ar-H)，7.31(t，J＝7.2Hz，2H，Ar-H)，7.07-6.97(m，2H，Ar-H)，6.29(s，1H，2-Ind-H)，4.32-4.21(m，1H，IndCH
2CH
2Flu)，4.18-4.00(m，2H，IndCH
2CH
2Flu)，3.73-3.64(m，1H，IndCH
2CH
2Flu)，2.88(t，J＝7.6Hz，1H，Cy-H)，2.00(d，J＝12.8Hz，1H，Cy-H)，1.78-1.64(m，3H，Cy-H)，1.50(d，J＝12Hz，1H，Cy-H)，1.43-1.26(m，2H，Cy-H)，1.26-1.08(m，2H，Cy-H)，0.94(ddd.J＝25.2，12.4，2.8Hz，1H，Cy-H).
Embodiment 6
Under propylene atmosphere in the autoclave of 100mL, drop into catalyzer C1 (1.25 μ mol), add the toluene solution of 4000 normal MAO, adding toluene then, to make the polymerization cumulative volume be 25mL, is forced into 0.6MPa, 100 ℃ of stirring reaction 30min.Reaction finishes, and uses the methyl alcohol termination reaction, send GC to analyze filtrate after the filtration, gets the C6 activity: 8.9 * 10
4G C
6/ (mol Zrh), 2-Methyl-1-pentene selectivity 97.8%.
Embodiment 7
Under propylene atmosphere in the autoclave of 100mL, drop into catalyzer C1 (1.25 μ mol), add the toluene solution of 2000 normal MAO, adding toluene then, to make the polymerization cumulative volume be 25mL, is forced into 0.6MPa, 100 ℃ of stirring reaction 30min.Reaction finishes, and uses the methyl alcohol termination reaction, send GC to analyze filtrate after the filtration, gets C
6Active: 5.3 * 10
4G C
6/ (mol Zrh), 2-Methyl-1-pentene selectivity 97.6%.
Embodiment 8
Under propylene atmosphere in the autoclave of 100mL, drop into catalyzer C1 (1.25 μ mol), add the toluene solution of 2000 normal MAO, adding toluene then, to make the polymerization cumulative volume be 25mL, is forced into 0.6MPa, 110 ℃ of stirring reaction 30min.Reaction finishes, and uses the methyl alcohol termination reaction, send GC to analyze filtrate after the filtration, gets C
6Active: 3.1 * 10
4G C
6/ (mol Zrh), 2-Methyl-1-pentene selectivity 96.9%.
Embodiment 9
Under propylene atmosphere in the autoclave of 100mL, drop into catalyzer C2 (1.25 μ mol), add the toluene solution of 4000 normal MAO, adding toluene then, to make the polymerization cumulative volume be 25mL, is forced into 0.6MPa, 100 ℃ of stirring reaction 30min.Reaction finishes, and uses the methyl alcohol termination reaction, send GC to analyze filtrate after the filtration, gets C
6Active: 1.1 * 10
4G C
6/ (mol Zrh), 2-Methyl-1-pentene selectivity＞99%.
Embodiment 10
Under propylene atmosphere in the autoclave of 100mL, drop into catalyzer C2 (1.25 μ mol), add the toluene solution of 2000 normal MAO, adding toluene then, to make the polymerization cumulative volume be 25mL, is forced into 0.6MPa, 100 ℃ of stirring reaction 30min.Reaction finishes, and uses the methyl alcohol termination reaction, send GC to analyze filtrate after the filtration, gets C
6Active: 9.3 * 10
3G C
6/ (mol Zrh), 2-Methyl-1-pentene selectivity＞99%.
Embodiment 11
Under propylene atmosphere in the autoclave of 100mL, drop into catalyzer C2 (1.25 μ mol), add the toluene solution of 4000 normal MAO, adding toluene then, to make the polymerization cumulative volume be 25mL, is forced into 0.6MPa, 110 ℃ of stirring reaction 30min.Reaction finishes, and uses the methyl alcohol termination reaction, send GC to analyze filtrate after the filtration, gets C
6Active: 1.2 * 10
4G C
6/ (mol Zrh), 2-Methyl-1-pentene selectivity＞99%.
Embodiment 12
Under propylene atmosphere in the autoclave of 100mL, drop into catalyzer C3 (1.25 μ mol), add the toluene solution of 4000 normal MAO, adding toluene then, to make the polymerization cumulative volume be 25mL, is forced into 0.6MPa, 100 ℃ of stirring reaction 30min.Reaction finishes, and uses the methyl alcohol termination reaction, send GC to analyze filtrate after the filtration, gets C
6Active: 3.8 * 10
5G C
6/ (mol Zrh), 2-Methyl-1-pentene selectivity 98.2%.
Embodiment 13
Under propylene atmosphere in the autoclave of 100mL, drop into catalyzer C3 (1.25 μ mol), add the toluene solution of 2000 normal MAO, adding toluene then, to make the polymerization cumulative volume be 25mL, is forced into 0.6MPa, 100 ℃ of stirring reaction 30min.Reaction finishes, and uses the methyl alcohol termination reaction, send GC to analyze filtrate after the filtration, gets C
6Active: 2.6 * 10
5G C
6/ (mol Zrh), 2-Methyl-1-pentene selectivity 97.8%.
Embodiment 14
Under propylene atmosphere in the autoclave of 100mL, drop into catalyzer C3 (1.25 μ mol), add the toluene solution of 2000 normal MAO, adding toluene then, to make the polymerization cumulative volume be 25mL, is forced into 0.6MPa, 110 ℃ of stirring reaction 30min.Reaction finishes, and uses the methyl alcohol termination reaction, send GC to analyze filtrate after the filtration, gets C
6Active: 2.4 * 10
5G C
6/ (mol Zrh), 2-Methyl-1-pentene selectivity 97.9%.
Embodiment 15
Under propylene atmosphere in the autoclave of 100mL, drop into catalyzer C4 (1.25 μ mol), add the toluene solution of 4000 normal MAO, adding toluene then, to make the polymerization cumulative volume be 25mL, is forced into 0.6MPa, 100 ℃ of stirring reaction 30min.Reaction finishes, and uses the methyl alcohol termination reaction, send GC to analyze filtrate after the filtration, gets C
6Active: 1.8 * 10
5C
6/ (mol Zrh), 2-Methyl-1-pentene selectivity 92.7%.
Embodiment 16
Under propylene atmosphere in the autoclave of 100mL, drop into catalyzer C4 (1.25 μ mol), add the toluene solution of 2000 normal MAO, adding toluene then, to make the polymerization cumulative volume be 25mL, is forced into 0.6MPa, 100 ℃ of stirring reaction 30min.Reaction finishes, and uses the methyl alcohol termination reaction, send GC to analyze filtrate after the filtration, gets C
6Active: 2.6 * 10
4G C
6/ (mol Zrh), 2-Methyl-1-pentene selectivity 82.1%.
Embodiment 17
Under propylene atmosphere in the autoclave of 100mL, drop into catalyzer C4 (1.25 μ mol), add the toluene solution of 2000 normal MAO, adding toluene then, to make the polymerization cumulative volume be 25mL, is forced into 0.6MPa, 110 ℃ of stirring reaction 30min.Reaction finishes, and uses the methyl alcohol termination reaction, send GC to analyze filtrate after the filtration, gets C
6Active: 8.5 * 10
4G C
6/ (mol Zrh), 2-Methyl-1-pentene selectivity 92.8%.
Embodiment 18
Under propylene atmosphere in the autoclave of 100mL, drop into catalyzer C5 (1.25 μ mol), add the toluene solution of 4000 normal MAO, adding toluene then, to make the polymerization cumulative volume be 25mL, is forced into 0.6MPa, 100 ℃ of stirring reaction 30min.Reaction finishes, and uses the methyl alcohol termination reaction, send GC to analyze filtrate after the filtration, gets C
6Active: 7.4 * 10
5G C
6/ (mol Zrh), 2-Methyl-1-pentene selectivity 99%.
Embodiment 19
Under propylene atmosphere in the autoclave of 100mL, drop into catalyzer C5 (1.25 μ mol), add the toluene solution of 2000 normal MAO, adding toluene then, to make the polymerization cumulative volume be 25mL, is forced into 0.6MPa, 100 ℃ of stirring reaction 30min.Reaction finishes, and uses the methyl alcohol termination reaction, send GC to analyze filtrate after the filtration, gets C
6Active: 3.8 * 10
5G C
6/ (mol Zrh), 2-Methyl-1-pentene selectivity 99%.
Embodiment 20
Under propylene atmosphere in the autoclave of 100mL, drop into catalyzer C5 (1.25 μ mol), add the toluene solution of 2000 normal MAO, adding toluene then, to make the polymerization cumulative volume be 25mL, is forced into 0.6MPa, 110 ℃ of stirring reaction 30min.Reaction finishes, and uses the methyl alcohol termination reaction, send GC to analyze filtrate after the filtration, gets C
6Active: 6.3 * 10
5G C
6/ (mol Zrh), 2-Methyl-1-pentene selectivity 98.7%.
Claims (10)
1. ethidene bridged linkage indene fluorene zirconium compound is characterized in that having following general formula:
In the formula (I), R
1, R
2Represent C respectively
1～C
10Straight chain, branched-chain alkyl, R
1And R
2The formation ring texture also can link to each other; R
3Represent hydrogen, C
1～C
12Alkyl, the thiazolinyl of straight chain, side chain or ring texture.
2. ethidene bridged linkage indene fluorene zirconium compound according to claim 1 is characterized in that R
1, R
2Be respectively C
1～C
6The alkyl of straight chain, branched structure, R
1And R
2Also can be connected to ring and constitute C
4～C
8Cyclic alkyl; R
3Represent hydrogen, C
1～C
6The alkyl of straight chain, side chain, ring texture, thiazolinyl.
3. ethidene bridged linkage indene fluorene zirconium compound according to claim 1, R
1, R
2Be preferably methyl, R
1, R
2Link to each other and constitute cyclohexyl; R
3Be preferably hydrogen, normal-butyl, cyclohexyl, cyclohexenyl.
4. the preparation method of each described ethidene bridged linkage indene fluorene zirconium compound of claim 1～3 comprises the steps:
(1) ethylene bridge biindyl fluorenes ligand compound and the alkali alkyl compound shown in the formula II reacted in organic medium, generate two an alkali metal salts of ethylene bridge biindyl fluorenes part, temperature of reaction is-78～25 ℃, and the reaction times is 2～24 hours; Described alkali alkyl compound is selected from C
1～C
4Lithium alkylide;
(2) with two an alkali metal salts of the ethylene bridge biindyl fluorenes part of step (1) in organic medium with ZrCl
4Reaction, temperature of reaction is-78～25 ℃, the reaction times is 2～24 hours, collects target compound then from reaction product.
5. method according to claim 4 is characterized in that:
The mol ratio of ethylene bridge biindyl fluorenes ligand compound and alkali alkyl compound is: 1: 2～2.5;
Two an alkali metal salts and the ZrCl of ethylene bridge biindyl fluorenes part
4Mol ratio be: 1: 1～1.2.
6. method according to claim 4 is characterized in that, the preferred butyllithium of described alkali alkyl compound.
7. method according to claim 4 is characterized in that described organic medium is selected from one or more in tetrahydrofuran (THF), ether, toluene, benzene, chloroform, methylene dichloride and the sherwood oil.
8. the application of each described ethidene bridged linkage indene fluorene zirconium compound of claim 1～3 is characterized in that, is used for the dimerization of propylene.
9. application according to claim 8, it is characterized in that, with each described ethidene bridged linkage indene fluorene zirconium compound of claim 1～3 is Primary Catalysts, with the alkylaluminoxane is promotor, in organic medium, make propylene at 0～110 ℃, dimerization under 0.1～1.5MPa, promotor is 500～15000: 1 with the metal molar of Primary Catalysts than A1/Zr.
10. application according to claim 9 is characterized in that described organic medium is selected from one or more in normal hexane, normal heptane, hexanaphthene, benzene, toluene and the dimethylbenzene.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565404A (en) * | 2016-10-26 | 2017-04-19 | 华东理工大学 | Dimerization method for high activity and selectivity propylene |
| CN108126753A (en) * | 2017-12-26 | 2018-06-08 | 华东理工大学 | Application of a kind of metallocene compound in Allyl end groups oligomerization of propene object is prepared |
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|---|---|---|---|---|
| WO1999020664A2 (en) * | 1997-10-23 | 1999-04-29 | Minnesota Mining And Manufacturing Company | Elastic polypropylenes and catalysts for their manufacture |
| EP0962462A2 (en) * | 1998-06-01 | 1999-12-08 | SOLVAY POLYOLEFINS EUROPE - BELGIUM (Société Anonyme) | Novel asymmetric ethylene-bridged metallocenes useful as catalysts in the polymerization of olefins and process for preparing said metallocenes |
| CN1275985A (en) * | 1997-09-12 | 2000-12-06 | 菲利浦石油公司 | Bridge fluorenyl/indenyl metallocenes and the use thereof |
| CN101781337A (en) * | 2010-02-04 | 2010-07-21 | 华东理工大学 | Novel ethidene bridged linkage substituted indene fluorene zirconium compound, method for preparing same and application thereof |
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2011
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1275985A (en) * | 1997-09-12 | 2000-12-06 | 菲利浦石油公司 | Bridge fluorenyl/indenyl metallocenes and the use thereof |
| WO1999020664A2 (en) * | 1997-10-23 | 1999-04-29 | Minnesota Mining And Manufacturing Company | Elastic polypropylenes and catalysts for their manufacture |
| EP0962462A2 (en) * | 1998-06-01 | 1999-12-08 | SOLVAY POLYOLEFINS EUROPE - BELGIUM (Société Anonyme) | Novel asymmetric ethylene-bridged metallocenes useful as catalysts in the polymerization of olefins and process for preparing said metallocenes |
| CN101781337A (en) * | 2010-02-04 | 2010-07-21 | 华东理工大学 | Novel ethidene bridged linkage substituted indene fluorene zirconium compound, method for preparing same and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565404A (en) * | 2016-10-26 | 2017-04-19 | 华东理工大学 | Dimerization method for high activity and selectivity propylene |
| CN106565404B (en) * | 2016-10-26 | 2019-06-04 | 华东理工大学 | A kind of method of high activity selectivity propylene dimerization |
| CN108126753A (en) * | 2017-12-26 | 2018-06-08 | 华东理工大学 | Application of a kind of metallocene compound in Allyl end groups oligomerization of propene object is prepared |
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