CN101016318A - Multinuclear metallocene complex and application thereof - Google Patents
Multinuclear metallocene complex and application thereof Download PDFInfo
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- CN101016318A CN101016318A CN 200610154810 CN200610154810A CN101016318A CN 101016318 A CN101016318 A CN 101016318A CN 200610154810 CN200610154810 CN 200610154810 CN 200610154810 A CN200610154810 A CN 200610154810A CN 101016318 A CN101016318 A CN 101016318A
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Abstract
The invention discloses a new polynuclear metallocene complex and application in the catalytic polymeric ethylene, whose general molecular formula is Ar-bR, wherein Ar is non-substituted or substituted phenyl; R is substituted radical on Ar directly; b is the quantity of substituted radical R on Ar, which is integral between 2 and 6; when R is multiple, it can be different metallocene complexes mutually; Ar is core of multiple substituted radical R.
Description
Technical field
The present invention relates to a kind of new multinuclear metallocene complex, and the application of this multinuclear metallocene complex in olefinic polymerization.
Background technology
It is single that metallocene catalyst has the active centre, advantages such as the structure of polymkeric substance and molecular weight controllability, yet so become the olefin polymerization catalysis of the class excellent performance after Ziegler-Natta catalyst., because its resulting polymers narrow molecular weight distribution, processing difficulties, become one of major reason that hinders process of industrialization. in order to address this problem, people mix different metallocene compounds, make the polymerization of composite catalyst catalyzed alkene or the polymkeric substance of metallocene catalysis olefinic polymerization gained is mixed the molecular weight distribution of widening polymkeric substance, but this method tends to destroy the characteristics of metallocene catalyst self and increases cost.Therefore, in recent years, design, synthetic double-core or multinuclear metallocene compound become a big research focus of metallocene catalysis field of olefin polymerisation, owing to have a plurality of metal centers simultaneously in the catalyst molecule, in polymerization process, can form more than one active centre, thereby can obtain the polyolefine of wide molecular weight distribution or bimodal distribution. up to now, about the synthetic of dinuclear metallocene compounds and the application report in olefinic polymerization more, but relevant multinuclear nuclear metallocene compound synthesizing and the applied research in olefinic polymerization then considerably less.
Summary of the invention
The invention provides a kind of new multinuclear metallocene complex, higher catalytic activity is arranged in olefinic polymerization.
A kind of multinuclear metallocene complex has following general molecular formula:
Ar—bR
Wherein, Ar is the phenyl that does not replace or replace, and the phenyl of replacement has at least one following substituting group: C
1～C
8Alkyl, C
3～C
8Cycloalkyl, halogen atom; The phenyl that replaces preferably has at least one following substituting group C
1～C
4Alkyl, halogen atom;
R represents directly to be connected in the substituting group on the Ar, and b represents directly to be connected in the quantity of the substituent R on the Ar, and b is 2～6 integer, when having a plurality of substituent R simultaneously, is nuclear with Ar all, and a plurality of substituent R can be different, and substituent R has following general formula:
R wherein
1Directly link to each other R with Ar
1Be C
1～C
8Alkylidene group, C
3～C
8Cycloalkylidene, C
1～C
8Halo alkylidene group, C
6～C
20Inferior aralkyl, C
1～C
8Alkylene oxide group, C
6～C
20Inferior aryloxy; Preferred C
1～C
4Alkylidene group; Methylene radical most preferably;
Cp
1, Cp
2Be separate do not replace or replace have cyclopentadiene, indenes or a fluorene structured part; The cyclopentadiene, indenes or the fluorene structured part that replace have at least one following substituting group: C
1～C
8Alkyl, C
3～C
8Cycloalkyl, C
6～C
20Aralkyl; Preferred C
1～C
4Alkyl; Most preferable.
M is Ti, Zr, Hf; Preferred Ti;
N is the integer of being determined by the Oxidation Number of metallic element M;
X is halogen, C
1～C
6Alkyl, C
6～C
20Aryl or C
6～C
20Substituted aryl, the aryl of described replacement has at least one following substituting group: C
1～C
8Alkyl, C
3～C
8Cycloalkyl, halogen atom; Preferred halogen; Cl most preferably;
Described multinuclear metallocene complex, most preferably following three kinds:
C
6H
3[CH
2C
5H
4Ti (C
5H
5) Cl
2]
3Structural formula is as follows:
C
6H
3[CH
2C
5H
4Ti (C
5H
4CH
3) Cl
2]
3Structural formula as follows:
C
6H
2[CH
2C
5H
4Ti (C
5H
5) Cl
2]
4Structural formula as follows:
The invention provides a kind of catalyzer, form by described multinuclear metallocene complex and organo-aluminium compound, the consumption of organo-aluminium compound and multinuclear metallocene complex is with the molar ratio computing of the metallic element M in the Al/ multinuclear metallocene complex, for Al/M is 500～10000, preferred 1000～1500;
Described organo-aluminium compound is a methylaluminoxane.
The present invention also provides the purposes of described catalyzer in the catalyzed ethylene polymerization reaction.Use multinuclear metallocene complex catalyzed ethylene polymerization in homogeneous phase of the present invention, in polymerization reactor, add solvent, organo-aluminium compound successively, feed ethylene gas, when temperature reached set(ting)value, the solution that adds bridging multinuclear cyclopentadiene titanium compound caused ethylene polymerization.Behind the reaction setting-up time, add the mixing solutions termination reaction of ethanol and hydrochloric acid, adularescent polyethylene precipitation generates immediately.Filter, polyethylene is removed catalyzer and the oven dry of acid back that participates in ethanol and distilled water wash.
1,3,5-three (cyclopentadiene methylene) benzene C
6H
3(CH
2C
5H
5)
3-1,3,5 (1) synthesize
To contain 1,3, the tetrahydrofuran solution of 5-three (brooethyl) benzene [1,3,5-tris (bromomethyl) benzene] is added drop-wise in the tetrahydrofuran solution that contains the cyclopentadienyl sodium salt stirring reaction.After removing solvent, add distilled water and ether in the residue, separatory, water are used the extracted with diethyl ether after drying more respectively.The vacuum removal solvent obtains faint yellow oily ligand 1, and 3,5-three (cyclopentadiene methylene) benzene (1).
Method with synthetic (1) synthesizes 1,2,4,5-four (cyclopentadiene methylene) benzene C
6H
2(CH
2C
5H
5)
4-1,2,4,5 (2)
Bridging three nuclears two cyclopentadiene titanium compound C
6H
3[CH
2C
5H
4Ti (C
5H
5) Cl
2]
3-1,3,5 (3) synthesize
The hexane solution of butyllithium is added drop-wise to contains 1,3,5-three (cyclopentadiene methylene) benzene [C
6H
3(CH
2C
5H
5)
3-1,3,5] in (1) diethyl ether solution, the limit edged stirs, and adds the back and is warming up to room temperature naturally, and stirring is spent the night, and filters, and with ether washing three times, vacuum-drying obtains pale yellow powder shape three lithium salts to solid respectively.This powder is slowly joined in the toluene solution of single luxuriant titanium, the limit edged stirs, and adds the back and is warming up to room temperature naturally, and stirring is spent the night, and filters solid methylene dichloride extracting, vacuum concentration, concentrated frozen crystallization.Filtration, vacuum-drying obtain red powder shape solid (3)
With methyl substituted bridging three nuclears two cyclopentadiene titanium compound C are arranged on the synthetic luxuriant ring of the method for synthetic (3)
6H
3[CH
2C
5H
4Ti (C
5H
4CH
3) Cl
2]
3-1,3,5 (4)
With synthetic bridging four nuclears of the method for synthetic (3) two cyclopentadiene titanium compounds
C
6H
2[CH
2C
5H
4Ti(C
5H
5)Cl
2]
4-1，2，4，5(5)
Find by a large amount of experiments, use bridging multinuclear metallocene complex catalyzed ethylene polymerization in homogeneous phase of the present invention,
Catalytic activity is lower during low catalyst concentration, the poly molecular weight of gained is also lower, when catalyst concn reaches finite concentration, the poly molecular weight of catalytic activity and gained all reaches maximum value, along with the rising of catalyst concn, the poly molecular weight of catalytic activity and gained reduces gradually again.
When the mol ratio of Al/M is low, catalytic activity is lower, the poly molecular weight of gained is also lower, when the mol ratio of Al/M acquires a certain degree, the poly molecular weight of catalytic activity and gained reaches maximum value respectively, after this, along with the increase of the mol ratio of Al/M, the poly molecular weight of catalytic activity and gained reduces gradually.
Along with the rising of polymeric reaction temperature, the poly molecular weight of catalytic activity and gained all reduces gradually.
Along with the prolongation of polymerization reaction time, catalytic activity reduces gradually, and the poly molecular weight of gained strengthens gradually.
The polymkeric substance that uses catalyst ethene polymerization in homogeneous phase of the present invention reaction to obtain carries out molecular weight distribution and Micro-Structure Analysis, through gpc analysis: molecular weight of polyethylene distribute (MWD) be than wide many of the molecular weight of polyethylene distribution of general metallocene catalyst catalyzed polymerization gained.DSC and
13CNMR shows that the gained polyethylene is linear, high-crystallinity.
Description of drawings
Accompanying drawing 1 is compound bridging three nuclears two cyclopentadiene titanium compound C in the embodiment of the invention 6
6H
3[CH
2C
5H
4Ti (C
5H
5) Cl
2]
3-1,3,5 (3) and methylaluminoxane be that catalyst ethene polymerization in homogeneous phase reaction gained is poly
13The CNMR spectrogram;
Accompanying drawing 2 is for there being methyl substituted bridging three nuclears two cyclopentadiene titanium compound C on the luxuriant ring in the embodiment of the invention 20
6H
3[CH
2C
5H
4Ti (C
5H
4CH
3) Cl
2]
3-1,3,5 (4) and methylaluminoxane be that catalyst ethene polymerization in homogeneous phase reaction gained is poly
13The CNMR spectrogram;
Accompanying drawing 3 is compound bridging four nuclears two cyclopentadiene titanium compound C in the embodiment of the invention 34
6H
2[CH
2C
5H
4Ti (C
5H
5) Cl
2]
4-1,2,4,5 (5) and methylaluminoxane be that catalyst ethene polymerization in homogeneous phase reaction gained is poly
13The CNMR spectrogram;
Among each figure:
X-coordinate is represented: chemical shift (ppm)
Ordinate zou is represented: absorption intensity
Embodiment
Embodiment 1
1,3,5-three (cyclopentadiene methylene) benzene C
6H
3(CH
2C
5H
5)
3-1,3,5 (1) synthesize
Under argon shield, under-78 ℃; to contain 1 of 1.79g (5mmol); 3; 5-three (brooethyl) benzene [1; 3,5-tris (bromomethyl) benzene] the 40mL tetrahydrofuran solution be added drop-wise in the 30mL tetrahydrofuran solution that contains 15mmol cyclopentadienyl sodium salt, the limit edged stirs; add the back and be warming up to 0 ℃ naturally, continued stirring reaction two hours down at 0 ℃.The vacuum removal solvent adds 30ml distilled water and 30ml ether in the residue, separatory, water are used 30ml extracted with diethyl ether twice more respectively, merge the ether phase, with anhydrous magnesium sulfate or hydrolith drying.The vacuum removal solvent obtains faint yellow oily ligand 1, and 3,5-three (cyclopentadiene methylene) benzene (1) 1.49g, yield 95.5%.
1H NMR(CDCl
3，δ，ppm)：2.82-2.86[m，3H，CH
2(Cp)]，2.96-2.97[m，3H，CH
2(Cp)]，3.67-3.72(m，6H，CH
2)，5.96-6.41[m，9H，CH(Cp)]，6.83-6.89(m，3H，C
6H
3).EIMS(70eV)m/z(％)：312(79)[M]
+，248(33)，233(75)，167(50)，79(100)。
Embodiment 2
1,2,4,5-four (cyclopentadiene methylene) benzene C
6H
2(CH
2C
5H
5)
4-1,2,4,5 (2) synthesize
Under argon shield, under-78 ℃; to contain 1 of 1.69g (3.75mmol); 2,4,5-four (brooethyl) benzene [1; 2; 4,5-tetrakis (bromomethyl) benzene] the 40mL tetrahydrofuran solution be added drop-wise in the 30mL tetrahydrofuran solution that contains 15mmol cyclopentadienyl sodium salt, the limit edged stirs; add the back and be warming up to 0 ℃ naturally, continued stirring reaction two hours down at 0 ℃.The vacuum removal solvent adds 30ml distilled water and 30ml ether in the residue, separatory, water are used 30ml extracted with diethyl ether twice more respectively, merge the ether phase, with anhydrous magnesium sulfate or hydrolith drying.The vacuum removal solvent obtains faint yellow oily ligand 1, and 2,4,5-four (cyclopentadiene methylene) benzene (2) 1.38g, yield 94.5%.
1H NMR(CDCl
3，δ，ppm)：2.80-2.84[m，4H，CH
2(Cp)]，2.93-2.94[m，4H，CH
2(Cp)]，3.67-3.73(m，8H，CH
2)，5.84-6.44[m，12H，CH(Cp)]，6.90-6.99(m，2H，C
6H
2).EIMS(70eV)m/z(％)：390(100)[M]
+，325(20)，179(23)，79(24).
Embodiment 3
Bridging three nuclears two cyclopentadiene titanium compound C
6H
3[CH
2C
5H
4Ti (C
5H
5) Cl
2]
3-1,3,5 (3) synthesize
Under argon shield, under 0 ℃, the hexane solution of 5.6ml (9mmo, butyllithium concentration is 1.6mol/l) butyllithium is added drop-wise to contains 0.94g (3mmol) 1,3,5-three (cyclopentadiene methylene) benzene [C
6H
3(CH
2C
5H
5)
3-1,3,5] in (1) 50ml diethyl ether solution, the limit edged stirs, and adds the back and is warming up to room temperature naturally, and stirring is spent the night, and filters, and with 20ml ether washing three times, vacuum-drying obtains pale yellow powder shape three lithium salts to solid respectively.Under 0 ℃, this powder is slowly joined 60ml to be contained in the toluene solution of the single luxuriant titanium of 1.97g (9mmol), the limit edged stirs, add the back and be warming up to room temperature naturally, stirring is spent the night, and filters, solid is used 40ml methylene dichloride extracting 4 times respectively, merge extract, vacuum concentration, concentrated solution place-15 ℃ of refrigerator and cooled to freeze crystalline substance.Filtration, vacuum-drying obtain red powder shape solid (3) 1.12g, yield 43.4%.
C
39H
36Ti
3Cl
6：(861.02)
Results of elemental analyses: C, 54.55%; H, 4.20%.Calc.:C, 54.40%; H, 4.21%.
1HNMR (CDCl
3, δ, ppm): 4.04 (s, 6H, CH
2), 6.34 (t, J=2.4 Hz, 6H, C
5H
4), 6.44 (t, J=2.4Hz, 6H, C
5H
4), 6.50 (s, 15H, C
5H
5), 6.95 (s, 3H, C
6H
3).
Embodiment 4
Methyl substituted bridging three nuclears two cyclopentadiene titanium compounds are arranged on the luxuriant ring
C
6H
3[CH
2C
5H
4Ti (C
5H
4CH
3) Cl
2]
3-1,3,5 (4) synthesize
Under argon shield, under 0 ℃, the hexane solution of 5.6ml (9mmo, butyllithium concentration is 1.6mol/l) butyllithium is added drop-wise to contains 0.94g (3mmol) 1,3,5-three (cyclopentadiene methylene) benzene [C
6H
3(CH
2C
5H
5)
3-1,3,5] in (1) 50ml diethyl ether solution, the limit edged stirs, and adds the back and is warming up to room temperature naturally, and stirring is spent the night, and filters, and with 20ml ether washing three times, vacuum-drying obtains pale yellow powder shape three lithium salts to solid respectively.Under 0 ℃, this powder is slowly joined 60ml to be contained in the toluene solution of the luxuriant titanium of 2.10g (9mmol) methyl list, the limit edged stirs, add the back and be warming up to room temperature naturally, stirring is spent the night, and filters, solid is used 40ml methylene dichloride extracting 4 times respectively, merge extract, vacuum concentration, concentrated solution place-15 ℃ of refrigerator and cooled to freeze crystalline substance.Filtration, vacuum-drying obtain red powder shape solid (4) 1.11g, yield 41.0%.
C
42H
42Ti
3Cl
6：(903.10)
Results of elemental analyses: C, 56.00%; H, 4.67%.Calc.:C, 55.86%; H, 4.69%.
1HNMR (CDCl
3, δ, ppm): 2.34 (s, 9H, CH
3), 4.01 (s, 6H, CH
2), 6.27-6.49 (m, 24H, C
5H
4), 6.94 (s, 3H, C
6H
3).
Embodiment 5
Bridging four nuclears two cyclopentadiene titanium compound C
6H
2[CH
2C
5H
4Ti (C
5H
5) Cl
2]
4-1,2,4,5 (5) synthesize
Under argon shield, under 0 ℃, the hexane solution of 5.6ml (9mmo, butyllithium concentration is 1.6mol/l) butyllithium is added drop-wise to contains 0.88g (2.25mmol) 1,2,4,5-four (cyclopentadiene methylene) benzene [C
6H
2(CH
2C
5H
5)
4-1,2,4,5] in (2) 50ml diethyl ether solution, the limit edged stirs, and adds the back and is warming up to room temperature naturally, and stirring is spent the night, and filters, and with 20ml ether washing three times, vacuum-drying obtains pale yellow powder shape four lithium salts to solid respectively.Under 0 ℃, this powder is slowly joined 60ml to be contained in the toluene solution of the single luxuriant titanium of 1.97g (9mmol), the limit edged stirs, add the back and be warming up to room temperature naturally, stirring is spent the night, and filters, solid is used 40ml methylene dichloride extracting 4 times respectively, merge extract, vacuum concentration, concentrated solution place-15 ℃ of refrigerator and cooled to freeze crystalline substance.Filtration, vacuum-drying obtain red powder shape solid (5) 0.89g, yield 35.2%.
C
50H
46Ti
4Cl
8：(1121.99)
Results of elemental analyses: C, 53.69%; H, 4.1 7%.Calc.:C, 53.52%; H, 4.13%.
1HNMR (CDCl
3, δ, ppm): 4.02 (s, 8H, CH
2), 6.35 (t, J=2.4Hz, 8H, C
5H
4), 6.43 (t, J=2.4Hz, 8H, C
5H
4), 6.53 (s, 20H, C
5H
5), 6.91 (s, 2H, C
6H
2).
Embodiment 6～19
With bridging three nuclear two cyclopentadiene titanium compounds (3) C
6H
3[CH
2C
5H
4Ti (C
5H
5) Cl
2]
3With methylaluminoxane be catalyst ethene polymerization in homogeneous phase reaction
In 50mL polyreaction bottle, add the toluene solution of toluene, 10% methylaluminoxane (MAO) successively, feed ethylene gas, the cumulative volume that institute adds liquid is 25ml,, the pressure of feeding ethene is 1 normal atmosphere (being 1bar).When temperature reached set(ting)value in the bottle, the toluene solution that adds bridging multinuclear two cyclopentadiene titanium compounds (3) caused ethylene polymerization.Behind the reaction setting-up time, add the mixing solutions termination reaction of 150ml ethanol and 10ml hydrochloric acid, adularescent polyethylene precipitation generates immediately.Filter, polyethylene is removed catalyzer and the acid that participates in ethanol and distilled water wash repeatedly, is dried to constant weight in 60 ℃ of vacuum drying ovens.
Reaction conditions and result such as table 1:
Table 1
| The embodiment sequence number | Catalyst concn ((10 -4mol Ti/ L)) | Catalyst ratio n (Al)/n (Ti) | Temperature of reaction (℃) | Reaction times (min) | Reactive behavior (10 4g of PE/(mol Ti h) | Molecular weight of product (10 4) |
| 6 | 0.5 | 1000 | 40 | 0.5 | 4.00 | 18.60 |
| 7 | 1.0 | 1000 | 40 | 0.5 | 5.33 | 28.80 |
| 8 | 1.5 | 1000 | 40 | 0.5 | 5.10 | 21.90 |
| 9 | 2.0 | 1000 | 40 | 0.5 | 3.70 | 14.00 |
| 10 | 1.0 | 500 | 40 | 0.5 | 2.67 | 22.40 |
| 11 | 1.0 | 1500 | 40 | 0.5 | 7.33 | 26.00 |
| 12 | 1.0 | 2000 | 40 | 0.5 | 6.33 | 22.90 |
| 13 | 1.0 | 1000 | 0 | 0.5 | 11.60 | 79.20 |
| 14 | 1.0 | 1000 | 20 | 0.5 | 6.23 | 29.00 |
| 15 | 1.0 | 1000 | 60 | 0.5 | 4.13 | 18.20 |
| 16 | 1.0 | 1000 | 80 | 0.5 | 1.77 | 3.89 |
| 17 | 1.0 | 1000 | 40 | 0.25 | 9.53 | 19.00 |
| 18 | 1.0 | 1000 | 40 | 0.75 | 4.53 | 29.50 |
| 19 | 1.0 | 1000 | 40 | 1.0 | 4.27 | 29.80 |
Catalytic activity is lower during low catalyst concentration, and the poly molecular weight of gained is also lower, when catalyst concn reaches 1.0 * 10
-4During mol Ti/L, the poly molecular weight of catalytic activity and gained all reaches maximum value, and along with the rising of catalyst concn, the poly molecular weight of catalytic activity and gained reduces gradually again.
When the mol ratio of Al/Ti is low, catalytic activity is lower, the poly molecular weight of gained is also lower, when the mol ratio of Al/Ti reaches 1500 and 1000, the poly molecular weight of catalytic activity and gained reaches maximum value respectively, after this, along with the increase of the mol ratio of Al/Ti, the poly molecular weight of catalytic activity and gained reduces gradually.
Along with the rising of polymeric reaction temperature, the poly molecular weight of catalytic activity and gained all reduces gradually.
Along with the prolongation of polymerization reaction time, catalytic activity reduces gradually, and the poly molecular weight of gained strengthens gradually.
Will be with bridging three nuclear two cyclopentadiene titanium compounds (3) C
6H
3[CH
2C
5H
4Ti (C
5H
5) Cl
2]
3With methylaluminoxane be that the polymkeric substance that catalyst ethene polymerization in homogeneous phase reaction obtains carries out molecular weight distribution and Micro-Structure Analysis
Through gpc analysis: molecular weight of polyethylene distribute (MWD) be 6.52, it is wide many to distribute than the molecular weight of polyethylene of general metallocene catalyst catalyzed polymerization gained.
It is 132.4 ℃ that DSC records the molten point of polyethylene (Tm), DSC and
13C NMR shows that the gained polyethylene is linear, high-crystallinity.
So that methyl substituted bridging three nuclear two cyclopentadiene titanium compounds (4) C to be arranged on the luxuriant ring
6H
3[CH
2C
5H
4Ti (C
5H
4CH
3) Cl
2]
3With methylaluminoxane be catalyst ethene polymerization in homogeneous phase reaction
In 50mL polyreaction bottle, the toluene solution that adds toluene, 10% methylaluminoxane (MAO) successively, feed ethylene gas, when temperature reaches set(ting)value in the bottle, add the toluene solution that methyl substituted bridging multinuclear two cyclopentadiene titanium compounds (4) are arranged on the luxuriant ring and cause ethylene polymerization.Behind the reaction setting-up time, add the mixing solutions termination reaction of 150ml ethanol and 10ml hydrochloric acid, adularescent polyethylene precipitation generates immediately.Filter, polyethylene is removed catalyzer and the acid that participates in ethanol and distilled water wash repeatedly, is dried to constant weight in 60 ℃ of vacuum drying ovens.
Reaction conditions and result such as table 2:
Table 2
| The embodiment sequence number | Catalyst concn ((10 -4mol Ti/ L)) | Catalyst ratio n (Al)/n (Ti) | Temperature of reaction (℃) | Reaction times (min) | Reactive behavior (10 4g of PE/(mol Ti h) | Molecular weight of product (10 4) |
| 20 | 0.5 | 1000 | 40 | 0.5 | 3.33 | 9.13 |
| 21 | 1.0 | 1000 | 40 | 0.5 | 3.83 | 12.54 |
| 22 | 1.5 | 1000 | 40 | 0.5 | 3.50 | 7.01 |
| 23 | 2.0 | 1000 | 40 | 0.5 | 3.40 | 7.42 |
| 24 | 1.0 | 500 | 40 | 0.5 | 2.27 | 8.68 |
| 25 | 1.0 | 1500 | 40 | 0.5 | 5.10 | 10.80 |
| 26 | 1.0 | 2000 | 40 | 0.5 | 5.03 | 9.00 |
| 27 | 1.0 | 1000 | 0 | 0.5 | 6.10 | 41.90 |
| 28 | 1.0 | 1000 | 20 | 0.5 | 4.20 | 15.70 |
| 29 | 1.0 | 1000 | 60 | 0.5 | 2.23 | 3.43 |
| 30 | 1.0 | 1000 | 80 | 0.5 | 1.43 | 2.10 |
| 31 | 1.0 | 1000 | 40 | 0.25 | 6.30 | 7.10 |
| 32 | 1.0 | 1000 | 40 | 0.75 | 2.77 | 13.00 |
| 33 | 1.0 | 1000 | 40 | 1.0 | 2.47 | 13.20 |
Catalytic activity is lower during low catalyst concentration, and the poly molecular weight of gained is also lower, when catalyst concn reaches 1.0 * 10
-4During mol Ti/L, the poly molecular weight of catalytic activity and gained all reaches maximum value, and along with the rising of catalyst concn, the poly molecular weight of catalytic activity and gained reduces gradually again.
When the mol ratio of Al/Ti is low, catalytic activity is lower, the poly molecular weight of gained is also lower, when the mol ratio of Al/Ti reaches 1500 and 1000, the poly molecular weight of catalytic activity and gained reaches maximum value respectively, after this, along with the increase of the mol ratio of Al/Ti, the poly molecular weight of catalytic activity and gained reduces gradually.
Along with the rising of polymeric reaction temperature, the poly molecular weight of catalytic activity and gained all reduces gradually.
Along with the prolongation of polymerization reaction time, catalytic activity reduces gradually, and the poly molecular weight of gained strengthens gradually.
Will be so that methyl substituted bridging three nuclear two cyclopentadiene titanium compounds (4) C to be arranged on the luxuriant ring
6H
3[CH
2C
5H
4Ti (C
5H
4CH
3) C1
2]
3With methylaluminoxane be that the polymkeric substance that catalyst ethene polymerization in homogeneous phase reaction obtains carries out molecular weight distribution and Micro-Structure Analysis
Through gpc analysis: molecular weight of polyethylene distribute (MWD) be 9.54, it is wide many to distribute than the molecular weight of polyethylene of general metallocene catalyst catalyzed polymerization gained.
It is 131.6 ℃ that DSC records the molten point of polyethylene (Tm), DSC and
13C NMR shows that the gained polyethylene is linear, high-crystallinity.
Embodiment 34～50
With bridging four nuclear two cyclopentadiene titanium compounds (5) C
6H
2[CH
2C
5H
4Ti (C
5H
5) Cl
2]
4With methylaluminoxane be catalyst ethene polymerization in homogeneous phase reaction
In 50mL polyreaction bottle, add the toluene solution of toluene, 10% methylaluminoxane (MAO) successively, feed ethylene gas, when temperature reached set(ting)value in the bottle, the toluene solution that adds bridging multinuclear two cyclopentadiene titanium compounds (5) caused ethylene polymerization.Behind the reaction setting-up time, add the mixing solutions termination reaction of 150ml ethanol and 10ml hydrochloric acid, adularescent polyethylene precipitation generates immediately.Filter, polyethylene is removed catalyzer and the acid that participates in ethanol and distilled water wash repeatedly, is dried to constant weight in 60 ℃ of vacuum drying ovens.
Reaction conditions and result such as table 3:
Table 3
| The embodiment sequence number | Catalyst concn ((10 -4mol Ti/ L)) | Catalyst ratio n (Al)/n (Ti) | Temperature of reaction (℃) | Reaction times (min) | Reactive behavior (10 4g of PE/(mol Ti h) | Molecular weight of product (10 4) |
| 34 | 0.5 | 1000 | 40 | 0.5 | 3.83 | 9.65 |
| 35 | 1.0 | 1000 | 40 | 0.5 | 3.88 | 20.00 |
| 36 | 1.5 | 1000 | 40 | 0.5 | 4.47 | 17.50 |
| 37 | 2.0 | 1000 | 40 | 0.5 | 4.10 | 13.70 |
| 38 | 1.0 | 500 | 40 | 0.5 | 2.93 | 18.30 |
| 39 | 1.0 | 1000 | 40 | 0.5 | 3.88 | 20.00 |
| 40 | 1.0 | 1500 | 40 | 0.5 | 6.33 | 21.60 |
| 41 | 1.0 | 2000 | 40 | 0.5 | 5.28 | 19.10 |
| 42 | 1.0 | 1000 | 0 | 0.5 | 6.25 | 71.20 |
| 43 | 1.0 | 1000 | 20 | 0.5 | 4.30 | 27.20 |
| 44 | 1.0 | 1000 | 40 | 0.5 | 3.88 | 20.00 |
| 45 | 1.0 | 1000 | 60 | 0.5 | 3.73 | 12.20 |
| 46 | 1.0 | 1000 | 80 | 0.5 | 1.50 | 4.24 |
| 47 | 1.0 | 1000 | 40 | 0.25 | 7.28 | 8.94 |
| 48 | 1.0 | 1000 | 40 | 0.5 | 3.88 | 20.00 |
| 49 | 1.0 | 1000 | 40 | 0.75 | 3.15 | 21.90 |
| 50 | 1.0 | 1000 | 40 | 1.0 | 3.13 | 21.01 |
Catalytic activity is lower during low catalyst concentration, and the poly molecular weight of gained is also lower, when catalyst concn reaches 1.5 * 10
-4Mol Ti/L and 1.5 * 10
-4During mol Ti/L, the poly molecular weight of catalytic activity and gained reaches maximum value respectively, and after this, along with the rising of catalyst concn, the poly molecular weight of catalytic activity and gained reduces gradually.
When the mol ratio of Al/Ti is low, catalytic activity is lower, the poly molecular weight of gained is also lower, when the mol ratio of Al/Ti reaches 1500, the poly molecular weight of catalytic activity and gained all reaches maximum value, after this, along with the increase of the mol ratio of Al/Ti, the poly molecular weight of catalytic activity and gained reduces gradually.
Along with the rising of polymeric reaction temperature, the poly molecular weight of catalytic activity and gained all reduces gradually.
Along with the prolongation of polymerization reaction time, catalytic activity reduces gradually, and the poly molecular weight of gained strengthens gradually.
Will be with bridging four nuclear two cyclopentadiene titanium compounds (5) C
6H
2[CH
2C
5H
4Ti (C
5H
5) Cl
2]
4With methylaluminoxane be that the polymkeric substance that catalyst ethene polymerization in homogeneous phase reaction obtains carries out molecular weight distribution and Micro-Structure Analysis
Through gpc analysis: molecular weight of polyethylene distribute (MWD) be 16.54, it is wide many to distribute than the molecular weight of polyethylene of traditional metallocene catalyst catalyzed polymerization gained.
It is 132.4 ℃ that DSC records the molten point of polyethylene (Tm), DSC and
13C NMR shows that the gained polyethylene is linear, high-crystallinity.
Claims (6)
1, a kind of multinuclear metallocene complex is characterized in that: have following general molecular formula:
Ar-bR
Wherein, Ar is the phenyl that does not replace or replace, and the phenyl of replacement has at least one following substituting group: C
1～C
8Alkyl, C
3～C
8Cycloalkyl, halogen atom;
R represents directly to be connected in the substituting group on the Ar, and b represents directly to be connected in the quantity of the substituent R on the Ar, and b is 2～6 integer, when having a plurality of substituent R simultaneously, is nuclear with Ar all, and a plurality of substituent R can be different, and substituent R has following general formula:
R wherein
1Directly link to each other R with Ar
1Be C
1～C
8Alkylidene group, C
3～C
8Cycloalkylidene, C
1～C
8Halo alkylidene group, C
6～C
20Inferior aralkyl, C
1～C
8Alkylene oxide group, C
6～C
20Inferior aryloxy;
Cp
1, Cp
2Be separate do not replace or replace have cyclopentadiene, indenes or a fluorene structured part, the cyclopentadiene of replacement, indenes or fluorene structured part have at least one following substituting group: C
1～C
8Alkyl, C
3～C
8Cycloalkyl, C
6～C
20Aralkyl,
M is Ti, Zr, Hf;
N is the integer of being determined by the Oxidation Number of metallic element M;
X is halogen, C
1～C
6Alkyl, C
6～C
20Aryl or C
6～C
20Substituted aryl, the aryl of described replacement has at least one following substituting group: C
1～C
8Alkyl, C
3～C
8Cycloalkyl, halogen atom;
2, multinuclear metallocene complex as claimed in claim 1 is characterized in that: have following general molecular formula:
Ar-bR
Wherein, Ar is the phenyl that does not replace or replace, and the phenyl of replacement has at least one following substituting group: C
1～C
4Alkyl, halogen atom;
R represents directly to be connected in the substituting group on the Ar, and b represents directly to be connected in the quantity of the substituent R on the Ar, and b is 2～6 integer, when having a plurality of substituent R simultaneously, is nuclear with Ar all, and a plurality of substituent R can be different, and substituent R has following general formula:
R wherein
1Directly link to each other R with Ar
1Be C
1～C
4Alkylidene group;
Cp
1, Cp
2Be separate do not replace or replace have cyclopentadiene, indenes or fluorene structured part, the cyclopentadiene of replacement, indenes or a fluorene structured part Cp
1, Cp
2Has at least one C
1～C
4Alkyl;
M is Ti;
n＝2
X is a halogen.
3, as claim 1,2 described multinuclear metallocene complexes, it is characterized in that: molecular formula is C
6H
3[CH
2C
5H
4Ti (C
5H
5) Cl
2]
3, C
6H
3[CH
2C
5H
4Ti (C
5H
4CH
3) Cl
2]
3, or C
6H
2[CH
2C
5H
4Ti (C
5H
5) Cl
2]
4
C wherein
6H
3[CH
2C
5H
4Ti (C
5H
5) Cl
2]
3Structural formula as follows:
C
6H
3[CH
2C
5H
4Ti (C
5H
4CH
3) Cl
2]
3Structural formula as follows:
C
6H
2[CH
2C
5H
4Ti (C
5H
5) Cl
2]
4Structural formula as follows:
4, a kind of catalyzer that contains multinuclear metallocene complex as claimed in claim 1, it is characterized in that: described catalyzer is made up of multinuclear metallocene complex and methylaluminoxane, the consumption of methylaluminoxane and multinuclear metallocene complex is with the molar ratio computing of the metallic element M in Al and the multinuclear metallocene complex, for Al/M is 500～10000.
5, catalyzer as claimed in claim 4 is characterized in that: the consumption of methylaluminoxane and multinuclear metallocene complex is with the molar ratio computing of the metallic element M in Al and the multinuclear metallocene complex, for Al/M is 1000～1500.
6, as claim 4, the application of 5 described catalyzer in the catalyzed ethylene polymerization reaction.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103232589A (en) * | 2013-04-27 | 2013-08-07 | 大连理工大学 | Poly1,4-di(cyclopentadienyl methylene)benzene and preparation method thereof |
| CN103242127A (en) * | 2013-04-10 | 2013-08-14 | 大连理工大学 | Cyclopentadiene derivative 1,4-bis(cyclopentadiene methylene) benzene and preparation method thereof |
| CN115260738A (en) * | 2022-08-06 | 2022-11-01 | 苏州大学 | Thermal-oxidation-resistant thermoplastic polyurethane and preparation method thereof |
-
2006
- 2006-11-17 CN CNB2006101548108A patent/CN100491386C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242127A (en) * | 2013-04-10 | 2013-08-14 | 大连理工大学 | Cyclopentadiene derivative 1,4-bis(cyclopentadiene methylene) benzene and preparation method thereof |
| CN103232589A (en) * | 2013-04-27 | 2013-08-07 | 大连理工大学 | Poly1,4-di(cyclopentadienyl methylene)benzene and preparation method thereof |
| CN115260738A (en) * | 2022-08-06 | 2022-11-01 | 苏州大学 | Thermal-oxidation-resistant thermoplastic polyurethane and preparation method thereof |
| CN115260738B (en) * | 2022-08-06 | 2024-03-19 | 苏州大学 | Thermo-oxidative-resistant thermoplastic polyurethane and preparation method thereof |
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