CN101638422B - Bis-silicon-bridged metallocene compound, preparation method and application thereof - Google Patents

Bis-silicon-bridged metallocene compound, preparation method and application thereof Download PDF

Info

Publication number
CN101638422B
CN101638422B CN200810117484A CN200810117484A CN101638422B CN 101638422 B CN101638422 B CN 101638422B CN 200810117484 A CN200810117484 A CN 200810117484A CN 200810117484 A CN200810117484 A CN 200810117484A CN 101638422 B CN101638422 B CN 101638422B
Authority
CN
China
Prior art keywords
silicon
bis
2mol
bridged metallocene
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN200810117484A
Other languages
Chinese (zh)
Other versions
CN101638422A (en
Inventor
米普科
钱锦华
王斯晗
许胜�
李建忠
张德顺
邢秋菊
张宝军
刘敏
曲家波
张琰
陈谦
阎修维
王桂芝
卢攀峰
韩雪梅
江玲
孙淑坤
杨俊凤
李玉龙
黄付玲
王亚丽
王秀慧
王力搏
张志凤
张婧元
张学业
张文超
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
East China University of Science and Technology
China Petroleum and Natural Gas Co Ltd
Original Assignee
East China University of Science and Technology
China Petroleum and Natural Gas Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by East China University of Science and Technology, China Petroleum and Natural Gas Co Ltd filed Critical East China University of Science and Technology
Priority to CN200810117484A priority Critical patent/CN101638422B/en
Publication of CN101638422A publication Critical patent/CN101638422A/en
Application granted granted Critical
Publication of CN101638422B publication Critical patent/CN101638422B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The invention relates to a bis-silicon-bridged metallocene compound, a preparation method and application thereof. Substituents such as alkyl, alkenyl and silicon base are introduced to a double bridge ligand and a cyclopentadienyl ring of CpMC3, particularly to the double bridge ligand to obtain a series of bis-silicon-bridged metallocene compounds containing the substituents on the bridged cyclopentadienyl ring; the compound has a simple synthetic route, high product yield, and easy separation and purification and less needed cocatalyst when the compounds are used for catalyzing the copolymerization between ethylene such as ethylene/hexene-1, ethylene/octylene-1 and the like and long chain alpha-olefin; the compound has high catalytic activity, the long chain alpha-olefin has high insertion rate; the compound catalyzes the copolymerization of the ethylene/hexene-1, the polymerization activity is 3.22*106gPE/mol.cat.h., and the content of hexene-1 in a polymer is 6.83 percent; and the compound catalyzes the copolymerization of the ethylene/octylene-1, the polymerization activity is 2.64*106gPE/mol.cat.h., and the content of octylene-1 in the polymer is 5.26 percent.

Description

A kind of bis-silicon-bridged metallocene compound
Technical field
The present invention relates to contain on the luxuriant ring of a kind of bridging substituent bis-silicon-bridged metallocene compound and preparation method thereof and the application in vinyl polymerization, ethene/1-hexene and ethene/1-octene copolymer close.
Background technology
The fifties in last century, Ziegler-Natta (G.Natta; P.Ginnini, J.Am.Chem.Soc., 1954,79:2975) catalyzer successfully is applied to ethene, propylene polymerization; Since 1960; A large amount of novel metal organic cpds is synthetic by successfully; For industry provides a series of high reactivities, highly selective new catalyst; Be widely used in alpha-olefin polymerization and various organic chemical reactions, also demonstrate huge vitality the synthetic of novel material and life science.
The eighties, and Kaminsky etc. (W.Kaminsky, M.Miri, H.Sinn, R.Woldt, Makromol.Common., 1983,4:417) find MAO (MAO) and Cp 2ZrMe 2The catalystsystem of forming is dissolved in the toluene, can homogeneous phase highly active catalytic vinyl polymerization, and activity reaches 40,000kgPE/g.Zr.h.At present, whole world polyolefine YO is up to tens million of tons, and economic benefit is very considerable, has become one of pillar industry in national economy, and therefore each big oil, chemical company drop into huge fund one after another in the world, research and development novel metal organic catalyst.
The metallocene catalyst that is used for olefinic polymerization comprises two types of single center and multicenters; The monokaryon metallocene catalyst is the emphasis of various countries scientist research always; Almost covered all respects of this research field, be difficult to big original innovation property by the monokaryon catalyzer of patent protection.Containing substituent doube bridge metallocene on the bridge chain is a brand-new research field, because of needed co-catalyst amount is little, therefore has great industrial application value.This area research is very active in recent years.It is higher to make every effort to the development research activity, and cost is lower, is used for containing substituent bis-silicon-bridged metallocene catalyst on the luxuriant ring of bridging of olefinic polymerization.
The compound of the titanium of unsubstituted on the bridge of bibliographical information similar structures is arranged, and structure is following:
Figure S2008101174842D00021
Do not see the report of relevant olefinic polymerization.
Also once there were report, structure such as figure below synthesizing of the compound of unsubstituted part trichlorine titanium on the bridge:
Do not see the report of relevant olefinic polymerization.
1996, people such as Jean L.Huhmann reported asymmetric double silicon-bridged dinuclear complex compound
Figure S2008101174842D00023
Do not see the report of relevant olefinic polymerization.
The example that two silicon bridge compounds of unsubstituted are applied to olefinic polymerization on the luxuriant ring of first bridging is reported by Lang
Figure S2008101174842D00024
This compound yield 45%, the polymerising ethylene result: vinyl monomer pressure is 1.0MPa, polymerization time 2.0 hours, promotor MAO: Ti=290, polymerization temperature is from 30 ℃-50 ℃, and activity is 2.16 * 10 5-3.00 * 10 5GPE/mol.Ti.h.
The synthetic doube bridge binuclear compound that mixes of king one hundred congruent people, a bridge is a carbon, another is silicon or germanium:
Figure S2008101174842D00031
R＝H，Me
M＝Ti，Zr
E＝Si，Ge
The vinyl polymerization result: 0.5 hour reaction times, vinyl monomer pressure 100kPa, MAO: Al=2500, M=Zr, 40 ℃ of polymerization temperatures, activity is 3.94 * 10 6GPE/mol.Zr.h.
CN1911945 discloses a kind of Bibridge binucleus cyclopentadienyl metal compound and preparation method thereof and in olefinic polymerization, has used.This patent can be used as catalyzer for restriction configuration Bibridge binucleus cyclopentadienyl metal compound, is used for the alhpa olefin copolymerization.Its general structure is following:
Figure S2008101174842D00032
Wherein: M represents Ti, Zr or Hf.R represents hydrogen, alkyl, aryl, thiazolinyl or alkoxyl group.
Obviously, there is not substituted radical on the luxuriant ring of the bridging of this compound.The catalyzer that above-mentioned document relates to, fashionable in catalyzed ethylene and long-chain alpha-olefin copolyreaction such as ethene/1-hervene copolymer, high reactivity is 3.59 * 10 5GPE/mol.M.h.atm (pressure is 1MPa), long-chain alpha-olefin insertion rate is up to 3.65%.
Summary of the invention
The present invention seeks to disclose on the luxuriant ring of a kind of bridging and contain substituent bis-silicon-bridged metallocene compound.The substituent bis-silicon-bridged metallocene that contains on the luxuriant ring of bridging produces two centers synergy, on luxuriant ring, introduces different substituents, effectively improves catalyst performance.
The said catalyst structure of the present invention is as follows:
Figure S2008101174842D00041
Wherein: M=Ti, Zr; R 2For hydrogen, contain the alkyl of 1～4 carbon atom, aryl, thiazolinyl; R 1Be the alkyl that contains 1～4 carbon atom, benzyl, allyl group, alkene butyl, silica-based etc., wherein allyl group, butyl are preferred group.
The preparation method of bis-silicon-bridged metallocene compound is characterized in that: following steps:
(1) with the 1mol dimethyldichlorosilane(DMCS) 0 ℃ down with the luxuriant sodium reaction of 2mol, through separate, dry, remove solvent, underpressure distillation, 40～42 ℃/2mmHg of collection cut obtains the weak yellow liquid product; Get the above-mentioned weak yellow liquid product of 1mol 0 ℃ of following and 2mol n-Butyl Lithium reaction, add the reaction of 1mol dimethyldichlorosilane(DMCS) again, get white crystal; Get the above-mentioned white crystal of 1mol; Adding 1000mL contains the hexane solution reaction of 2mol n-Butyl Lithium; Reacted 10～20 hours at-20 ℃～30 ℃ halogenide n-butyl bromide or the allyl bromide 98s that add 2mol then; Through desolventize, solid with the normal hexane extracting, concentrate, cooling, obtain the clear crystal product, be ligand L;
The ligand L structure is as follows:
Figure S2008101174842D00051
Wherein: R 1Be alkyl, benzyl, allyl group, the alkene butyl or silica-based that contains 1～4 carbon atom;
(2) get the tetrahydrofuran solution that 2000mL contains the 1mol ligand L, add the hexane solution that 1000mL contains the 2mol n-Butyl Lithium down, slowly rise to 25 ℃ at-40 ℃～0 ℃; Reacted 10～20 hours; Remove the solids that obtains that desolvates and dissolve with 3 liters of THFs, at 0 ℃～30 ℃ luxuriant titanium of trichlorine or the luxuriant zirconiums of trichlorine that add 2mol～2.2mol down, or trichlorine replaces luxuriant titanium or trichlorine replaces luxuriant zirconium; Reacted 2 hours～10 hours; Through desolventize, solids with dichloromethane extraction, concentrate, obtain solids-20 ℃ of crystallizations, be bis-silicon-bridged metallocene compound.
Can synthesize following compound with aforesaid method:
[μ，μ-(SiMe 2) 2(n-BuC 5H 2) 2)][(C 5H 5)TiCl 2] 2
[μ，μ-(SiMe 2) 2(Allyl-C 5H 2) 2)][(C 5H 5)TiCl 2] 2
[μ，μ-(SiMe 2) 2(n-BuC 5H 2) 2)][(C 5H 5)ZrCl 2] 2
[μ，μ-(SiMe 2) 2(Allyl-C 5H 2) 2)][(C 5H 5)ZrCl 2] 2
[μ，μ-(SiMe 2) 2(CH 3C 5H 2) 2)][(C 5H 5)ZrCl 2] 2
[μ，μ-(SiMe 2) 2(CH 3C 5H 2) 2)][(C 5H 5)TiCl 2] 2
[μ，μ-(SiMe 2) 2((CH 3) 3SiC 5H 2) 2)][(C 5H 5)ZrCl 2] 2
[μ，μ-(SiMe 2) 2(Allyl-C 5H 2) 2)][(Allyl-C 5H 5)ZrCl 2] 2
[μ，μ-(SiMe 2) 2(Allyl-C 5H 2) 2)][(Allyl-C 5H 5)TiCl 2] 2
[μ，μ-(SiMe 2) 2(Allyl-C 5H 2) 2)][(MeC 5H 5)TiCl 2] 2
[μ，μ-(SiMe 2) 2(Allyl-C 5H 2) 2)][(bezyl-C 5H 5)ZrCl 2] 2
[μ，μ-(SiMe 2) 2(bezyl-C 5H 2) 2)][(C 5H 5)ZrCl 2] 2
[μ，μ-(SiMe 2) 2(bezyl-C 5H 2) 2)][(Allyl-C 5H 5)ZrCl 2] 2
[μ，μ-(SiMe 2) 2(Allyl-C 5H 2) 2)][(MeC 5H 4)ZrCl 2] 2。
The present invention is at doube bridge part and CpMCl 3Luxuriant ring on; Particularly introduce alkyl, thiazolinyl, substituting group such as silica-based on the doube bridge part; Obtained containing substituent bis-silicon-bridged metallocene compound on the luxuriant ring of a series of bridging, improved the complex compound yield, catalyzed ethylene and long-chain alpha-olefin copolyreaction such as ethene/1-hexene, ethene/1-octene copolymer are fashionable; Olefin polymerizating activity is high, and the rate of long-chain alpha-olefin insertion simultaneously is higher.For example, under ethylene pressure 0.1MPa, be solvent, with complex compound [μ, μ-(SiMe with toluene 2) 2(CH 3CH 2CH 2CH 2-C 5H 2) 2)] [(C 5H 5) ZrCl 2] 2Be catalyzer, MAO is a promotor, and in 50 ℃ of 0.5 hour following reaction times of temperature of reaction, catalyzed ethylene/hexene-1 copolymerization is 957 at aluminium/zirconium ratio, and when hexene-1 concentration was 0.20mol/L, polymerization activity was 3.22 * 10 6GPE/mol.cat.h., hexene in the polymkeric substance-1 content 6.83%; Under similarity condition, catalyzed ethylene/octene-1 copolymerization, aluminium/zirconium ratio is 1050, when octene-1 concentration was 0.20mol/L, polymerization activity was 2.64 * 10 6GPE/mol.cat.h., octene-1 content 5.26% in the polymkeric substance.
The present invention adopts and contains substituent bis-silicon-bridged metallocene catalyst/MAO system on the luxuriant ring of bridging; Under low ratio promotor effect; Alpha-olefin copolymer is closed the acquisition high reactivity; Applicable to the homopolymerization or the copolymerization of terminal olefins such as ethene, be specially adapted to the copolymerization of ethene such as catalyzed ethylene/hexene-1, catalyzed ethylene/octene-1 and long-chain alpha-olefin.
See from the practical application of above-mentioned public technology scheme; It is obvious to contain substituent bis-silicon-bridged metallocene olefin polymerization catalysis advantage on the said bridge of the present invention: synthetic route is simple; Product yield is high, and separation and purification is easy, needs promotor few when being used for the copolymerization of ethene such as catalyzed ethylene/hexene-1, catalyzed ethylene/octene-1 and long-chain alpha-olefin; Catalytic activity is high, and long-chain alpha-olefin insertion rate is high.
Embodiment
Part is synthetic
Embodiment 1
Ligand L 1{ μ, μ-[(Me 2Si) 2(η 5-AllylC 5H 2) 2] synthetic
In the there-necked flask of a 500mL, add 50mL (0.42mol) (CH 3) 2SiCl 2, add the 100mL normal hexane again, stir.Under the ice-water bath condition, splash into the CpNa260mL (0.84mol) of 1.6M, reacted 6 hours, add the 50mL distilled water wash, go organic phase with the pear shape separatory funnel separatory, water merges organic phase, and uses anhydrous MgSO with the washing of 3 * 20mL ether 4Drying is filtered the vacuum removal solvent.40～42 ℃/2mmHg cut is collected in underpressure distillation, obtains weak yellow liquid product 18.05g; Said product is added in the Schlenk bottle of 250mL again, uses the 80mL n-hexane dissolution.Under ice-water bath, drip the about 53mL of 1.8M n-BuLi, stirring reaction 4 hours adds 11.6mL (CH again 3) 2SiCl 2And 20mLTHF, stirring reaction spends the night.React the postprecipitation that finishes, filter supernatant liquid, be concentrated into solid and separated out freezing and crystallizing then, get white crystal 16.5g; Get above-mentioned white crystal 100mmol, be dissolved in the 100mL THF, slowly add the hexane solution of the n-BuLi of 200mmol, obtain troubled liquor; Adopt the cooling of acetone liquid nitrogen bath, slowly add the allyl bromide 98 of 200mmol, heat up naturally; Reaction is spent the night, removal of solvent under reduced pressure, and residuum is used the normal hexane extracting; Concentrate, obtain clear crystal 45mmol, product yield 45%.
Embodiment 2
Ligand L 2{ μ, μ-[(Me 2Si) 2(η 5-BuC 5H 2) 2] synthetic
In the there-necked flask of a 500mL, add 50mL (0.42mol) (CH 3) 2SiCl 2, add the 100mL normal hexane again, stir.Under the ice-water bath condition, splash into the CpNa260mL (0.84mol) of 1.6M, reacted 6 hours, add the 50mL distilled water wash, go organic phase with the pear shape separatory funnel separatory, water merges organic phase, and uses anhydrous MgSO with the washing of 3 * 20mL ether 4Drying is filtered the vacuum removal solvent.40～42 ℃/2mmHg cut is collected in underpressure distillation, obtains weak yellow liquid product 18.05g; Said product is added in the Schlenk bottle of 250mL again, uses the 80mL n-hexane dissolution.Under ice-water bath, drip the about 53mL of 1.8M n-BuLi, stirring reaction 4 hours adds 11.6mL (CH again 3) 2SiCl 2And 20mLTHF, stirring reaction spends the night.React the postprecipitation that finishes, filter supernatant liquid, be concentrated into solid and separated out freezing and crystallizing then, get white crystal 16.5g; Get above-mentioned white crystal 100mmol, be dissolved in the 100mL THF, slowly add the hexane solution of the n-BuLi of 200mmol, obtain troubled liquor; Adopt the cooling of acetone liquid nitrogen bath, slowly add the n-butyl bromide of 200mmol, heat up naturally; Reaction is spent the night, removal of solvent under reduced pressure, and residuum is used the normal hexane extracting; Concentrate, obtain clear crystal 55mmol, product yield 55%.
Embodiment 3
Ligand L 3{ μ, μ-[(Me 2Si) 2(η 5-Me 3SiC 5H 2) 2] synthetic
Press embodiment 1 method equally, use Me 3SiCl replaces allyl bromide 98, can obtain ligand L 3{ μ, μ-[(Me 2Si) 2(η 5-Me 3SiC 5H 2) 2] white solid 52mmol, product yield 52%.
Embodiment 4
Ligand L 4 [μ, μ-(Me 2Si) 2(CH 3C 5H 3) 2)] synthetic
Press embodiment 1 method equally, replace allyl bromide 98, can obtain ligand L 4{ μ, μ-[(Me with methyl iodide 2Si) 2(η 5-CH 3C 5H 2) 2] white solid 35mmol, product yield 35%.
Complex compound is synthetic
Embodiment 5
Complex compound 1 [μ, μ-(SiMe 2) 2(H 2C=CHCH 2C 5H 2) 2)] [(C 5H 5) TiCl 2] 2Synthetic
Get ligand L 12.17g (6.7mmol), be dissolved in the 30mL normal hexane, coldcondition adds the hexane solution of the n-BuLi of 13.2mmol down, and stirring reaction spends the night, and elimination supernatant liquid, solid add the dissolving of 20mL THF, and low temperature adds the CpTiCl of 2.91g down 3, reaction is spent the night, removal of solvent under reduced pressure, and solid is used dichloromethane extraction, obtains garnet solid 1.6g, yield 36%.
Embodiment 6
Complex compound 2 [μ, μ-(SiMe 2) 2(H 2C=CHCH 2C 5H 2) 2)] [(C 5H 5) ZrCl 2] 2Synthetic
Ligand L 1640mg (2.00mmol) with 50mL THF dissolving, is dripped the n-BuLi hexane solution of 4.0mmol at normal temperatures, and it is muddy that reaction solution becomes gradually, gets white casse liquid, and stirring reaction spends the night, and obtains a large amount of white precipitates.Low temperature adds 1.6g CpZrCl rapidly 3.DME (4.0mmol), reaction solution becomes transparent faint yellow immediately, and reaction rises to room temperature gradually, continues stirred overnight.Vacuum is drained solvent, 20mLCH 2Cl 2Extraction, CH 2Cl 2/ n-Hexane recrystallization, low temperature is separated out white powder solid 730mg.Yield is 47%.
Embodiment 7
Complex compound 3 [μ, μ-(SiMe 2) 2(n-BuC 5H 2) 2)] [(C 5H 5) TiCl 2] 2Synthetic
Get ligand L 22.39g (6.7mmol), be dissolved in the 30mL normal hexane, coldcondition adds the hexane solution of the n-BuLi of 13.6mmol down, and stirring reaction spends the night, and elimination supernatant liquid, solid add the dissolving of 30mL THF, and low temperature adds the CpTiCl of 2.99g down 3, reaction is spent the night, removal of solvent under reduced pressure, and solid is used dichloromethane extraction, obtains garnet solid 1.9g, yield 39%.
Embodiment 8
Complex compound 4 [μ, μ-(SiMe 2) 2(n-BuC 5H 2) 2)] [(C 5H 5) ZrCl 2] 2Synthetic
According to the method for embodiment 7, use CpZrCl equally 3Replaced C pTiCl 3, reaction is spent the night, removal of solvent under reduced pressure, and solid is used dichloromethane extraction, obtains the white powder solid, yield 41%.
Embodiment 9
Complex compound 5 [μ, μ-(Me 2Si) 2(Me 3SiC 5H 2) 2] [CH 3CpTiCl 2] 2
According to the method for embodiment 7, replace ligand L 2 equally, use CH with ligand L 3 3CpTiCl 3Replaced C pTiCl 3, reaction is spent the night, removal of solvent under reduced pressure, and solid is used dichloromethane extraction, obtains the garnet solid, yield 38%.
Embodiment 10
Preparation [μ, μ-(SiMe 2) 2(CH 3CH 2CH 2CH 2-C 5H 2) 2)] [CH 3CpTiCl 2] 2
{ μ, μ-[(Me 2Si) 2(η 5-BuC 5H 3) 2] The preparation of part:
In there-necked flask, add the 1mol dimethyldichlorosilane(DMCS), add normal hexane again and stir.Under the ice-water bath condition, splash into luxuriant sodium 2mol, reacted 6 hours, add distilled water wash, go organic phase with the pear shape separatory funnel separatory, water merges organic phase, and uses anhydrous MgSO with the washing of 3 * 50mL ether 4Drying is filtered the vacuum removal solvent.40～42 ℃/2mmHg cut is collected in underpressure distillation, obtains the weak yellow liquid product; The above-mentioned weak yellow liquid product that obtains of 1mol is used n-hexane dissolution, under ice-water bath, drip the 2mol n-Butyl Lithium, stirring reaction 4 hours adds 2mol dimethyldichlorosilane(DMCS) and a small amount of THF reaction again.React the postprecipitation that finishes, filter supernatant liquid, be concentrated into solid and separated out freezing and crystallizing then, get white crystal, productive rate 71%.Get gained white crystal 1mol, be dissolved in the 2000mL THF, slowly add the hexane solution of 2mol n-Butyl Lithium, obtain troubled liquor; Adopt the cooling of acetone liquid nitrogen bath, in-20 ℃～20 ℃ n-butyl bromides that slowly add 2mol, natural temperature reaction; Removal of solvent under reduced pressure, solid are used the normal hexane extracting, concentrate; Cooling obtains clear crystal, product yield 55%.
[μ, μ-(SiMe 2 ) 2 (n-BuC 5 H 2 ) 2 )] [CH 3 CpTiCl 2 ] 2 Preparation:
Get above-mentioned { μ, the μ-[(Me that makes 2Si) 2(η 5-BuC 5H 3) 2] part 0.1mol, be dissolved in the 400mL normal hexane, at-40 ℃～0 ℃ hexane solution that adds the 0.2mol n-Butyl Lithium down, slowly rise to react about 25 ℃ and spend the night; Elimination supernatant liquid, solid add the dissolving of 300mL THF, at 0 ℃～30 ℃ luxuriant titanous chlorides of methyl that add 0.2mol～0.22mol down; Reaction is spent the night, removal of solvent under reduced pressure, and solid is used dichloromethane extraction; Obtain the garnet solid, be [μ, μ-(SiMe 2) 2(n-BuC 5H 2) 2)] [CH 3CpTiCl 2] 2Compound.
Homogeneous catalytic olefin polymerization under the normal pressure
Embodiment 11
The 100mL there-necked flask that magnetic agitation, gas tube will be arranged is with ethylene gas displacement 3 times, and constant temperature is 0.5 hour in 50 ℃ of thermostatic baths, adds toluene, 2.0 μ mol complex compound 5 [μ, μ-(Me successively 2Si) 2(Me 3SiC 5H 2) 2] [CH 3CpTiCl 2] 2, promotor MAO 2.5mL (1.50M) [Al/M=938], normal pressure feed ethylene gas, stirring reaction 30min down; Close the ethene gas cylinder, with 10% acidic alcohol termination reaction, polymkeric substance is transferred in the beaker; Hold over night is filtered, and washing with alcohol is to neutral; 80 ℃ of constant temperature drying under vacuum overnight, weighing polymer quality 1.56g, polymerization activity are 1.56 * 10 6G polymkeric substance/molcath.
Embodiment 12
The 100mL there-necked flask that magnetic agitation, gas tube will be arranged is with ethylene gas displacement 3 times, and constant temperature is 0.5 hour in 50 ℃ of thermostatic baths, adds toluene, 0.15mol/L hexene-1,2.0 μ mol complex compounds 1 successively; Promotor MAO 2.8mL (1.50M) [Al/M=1050], normal pressure feed ethene, stirring reaction 30min down; Close the ethene gas cylinder, with 10% acidic alcohol termination reaction, polymkeric substance is transferred in the beaker; Hold over night is filtered, and washing with alcohol is to neutral; 80 ℃ of constant temperature drying under vacuum overnight, weighing polymer quality 2.28g, polymerization activity are 2.28 * 10 6G polymkeric substance/molcath, hexene-1 content 4.06%.
Embodiment 13
The 100mL there-necked flask that magnetic agitation, gas tube will be arranged is with ethylene gas displacement 3 times, and constant temperature is 0.5 hour in 50 ℃ of thermostatic baths, adds toluene, 0.10mol/L hexene-1,2.0 μ mol complex compounds 2 successively; Promotor MAO 2.6mL (1.50M) [Al/M=975], normal pressure feed ethene, stirring reaction 30min down; Close the ethene gas cylinder, with 10% acidic alcohol termination reaction, polymkeric substance is transferred in the beaker; Hold over night is filtered, and washing with alcohol is to neutral; 80 ℃ of constant temperature drying under vacuum overnight, weighing polymer quality 2.78g, polymerization activity are 2.78 * 10 6G polymkeric substance/molcath, hexene-1 content 3.94%.
Embodiment 14
The 100mL there-necked flask that magnetic agitation, gas tube will be arranged is with ethylene gas displacement 3 times, and constant temperature is 0.5 hour in 50 ℃ of thermostatic baths, adds toluene, 0.15mol/L hexene-1,1.80 μ mol complex compounds 3 successively; Promotor MAO 2.6mL (1.50M) [Al/M=1083], normal pressure feed ethene, stirring reaction 30min down; Close the ethene gas cylinder, with 10% acidic alcohol termination reaction, polymkeric substance is transferred in the beaker; Hold over night is filtered, and washing with alcohol is to neutral; 80 ℃ of constant temperature drying under vacuum overnight, weighing polymer quality 1.85g, polymerization activity are 2.06 * 10 6G polymkeric substance/molcath, hexene-1 content 4.48%.
Embodiment 15
The 100mL there-necked flask that magnetic agitation, gas tube will be arranged is with ethylene gas displacement 3 times, and constant temperature is 0.5 hour in 50 ℃ of thermostatic baths, adds toluene, 0.20mol/L hexene-1,1.96 μ mol complex compounds 4 successively; Promotor MAO 2.5mL (1.50M) [Al/M=957], normal pressure feed ethene, stirring reaction 30min down; Close the ethene gas cylinder, with 10% acidic alcohol termination reaction, polymkeric substance is transferred in the beaker; Hold over night is filtered, and washing with alcohol is to neutral; 80 ℃ of constant temperature drying under vacuum overnight, weighing polymer quality 3.15g, polymerization activity are 3.22 * 10 6G polymkeric substance/molcath, hexene-1 content 6.83%.
Embodiment 16
The 100mL there-necked flask that magnetic agitation, gas tube will be arranged is with ethylene gas displacement 3 times, and constant temperature is 0.5 hour in 50 ℃ of thermostatic baths, adds toluene, 0.15mol/L octene-1,2.0 μ mol complex compounds 2 successively; Promotor MAO 2.7mL (1.50M) [Al/M=1012], normal pressure feed ethene, stirring reaction 30min down; Close the ethene gas cylinder, with 10% acidic alcohol termination reaction, polymkeric substance is transferred in the beaker; Hold over night is filtered, and washing with alcohol is to neutral; 80 ℃ of constant temperature drying under vacuum overnight, weighing polymer quality 2.12g, polymerization activity are 2.12 * 10 6G polymkeric substance/molcath, octene-1 content 4.27%.
Embodiment 17
The 150mL there-necked flask that magnetic agitation, gas tube will be arranged is with ethylene gas displacement 3 times, and constant temperature is 0.5 hour in 50 ℃ of thermostatic baths, adds toluene, 0.20mol/L octene-1,2.0 μ mol complex compounds 4 successively; Promotor MAO 2.8mL (1.50M) [Al/M=1050], normal pressure feed ethene, stirring reaction 30min down; Close the ethene gas cylinder, with 10% acidic alcohol termination reaction, polymkeric substance is transferred in the beaker; Hold over night is filtered, and washing with alcohol is to neutral; 80 ℃ of constant temperature drying under vacuum overnight, weighing polymer quality 2.63g, polymerization activity are 2.64 * 10 6G polymkeric substance/molcath, octene-1 content 5.26%.

Claims (3)

1. bis-silicon-bridged metallocene compound, it is characterized in that: general structure is as follows:
Figure FSB00000771300400011
Wherein: M=Ti, Zr;
R 1Be alkyl or the allyl group that contains 1～4 carbon atom;
R 2For hydrogen or contain the alkyl of 1～4 carbon atom.
2. the preparation method of the described bis-silicon-bridged metallocene compound of claim 1 is characterized in that: following steps:
(1) with the 1mol dimethyldichlorosilane(DMCS) 0 ℃ down with the luxuriant sodium reaction of 2mol, through separate, dry, underpressure distillation, 40～42 ℃/2mmHg of collection cut obtains weak yellow liquid; Get the above-mentioned weak yellow liquid of 1mol 0 ℃ of following and 2mol n-Butyl Lithium reaction, add the reaction of 1mol dimethyldichlorosilane(DMCS) again, get white crystal; Get the above-mentioned white crystal of 1mol; Adding 1000mL contains the hexane solution reaction of 2mol n-Butyl Lithium; Reacted 10～20 hours at-20 ℃～30 ℃ halogenide n-butyl bromide or the allyl bromide 98s that add 2mol then; Through desolventize, solid with the normal hexane extracting, concentrate, cooling, obtain the clear crystal product, be ligand L;
The ligand L structure is as follows:
Figure FSB00000771300400021
Wherein: R 1Be alkyl or the allyl group that contains 1～4 carbon atom;
(2) get the tetrahydrofuran solution that 2000mL contains the 1mol ligand L, add the hexane solution that 1000mL contains the 2mol n-Butyl Lithium down, slowly rise to 25 ℃ at-40 ℃～0 ℃; Reacted 10～20 hours; Remove the solids that obtains that desolvates and dissolve with 3 liters of THFs, at 0 ℃～30 ℃ luxuriant titanium of trichlorine or the luxuriant zirconiums of trichlorine that add 2mol～2.2mol down, or trichlorine replaces luxuriant titanium or trichlorine replaces luxuriant zirconium; Reacted 2 hours～10 hours; Through desolventize, solids with dichloromethane extraction, concentrate, obtain solids-20 ℃ of crystallizations, be bis-silicon-bridged metallocene compound.
A kind of bis-silicon-bridged metallocene compound according to claim 1 application, it is characterized in that: close catalyzer as vinyl polymerization, ethene/1-octene, ethene/1-hervene copolymer.
CN200810117484A 2008-07-31 2008-07-31 Bis-silicon-bridged metallocene compound, preparation method and application thereof Active CN101638422B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN200810117484A CN101638422B (en) 2008-07-31 2008-07-31 Bis-silicon-bridged metallocene compound, preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN200810117484A CN101638422B (en) 2008-07-31 2008-07-31 Bis-silicon-bridged metallocene compound, preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN101638422A CN101638422A (en) 2010-02-03
CN101638422B true CN101638422B (en) 2012-10-17

Family

ID=41613618

Family Applications (1)

Application Number Title Priority Date Filing Date
CN200810117484A Active CN101638422B (en) 2008-07-31 2008-07-31 Bis-silicon-bridged metallocene compound, preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN101638422B (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1911945A (en) * 2005-08-09 2007-02-14 华东理工大学 Bibridge binucleus cyclopentadienyl metal compound and its preparation method and application

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1911945A (en) * 2005-08-09 2007-02-14 华东理工大学 Bibridge binucleus cyclopentadienyl metal compound and its preparation method and application

Also Published As

Publication number Publication date
CN101638422A (en) 2010-02-03

Similar Documents

Publication Publication Date Title
CN105452268B (en) Metallocene compound, the carbon monoxide-olefin polymeric comprising it and the method for preparing olefin polymer using it
DE60226010T2 (en) MULTICOLORED METAL CELL CALCULATOR
CN106062012B (en) Support type mixed catalyst and the method for preparing the polymer based on alkene using it
CN105473601B (en) Metallocene compound, comprising its carbon monoxide-olefin polymeric and using it prepare the method for olefin polymer
CN104513280B (en) A kind of sPP bridged binuclear metallocene compounds and preparation method and application
WO2003082879A1 (en) Ionic aluminoxanate compositions and their use in catalysis
JP6029757B2 (en) Method for producing catalyst for polyolefin polymerization and method for producing polyolefin
US6825296B2 (en) Catalyst component for olefin polymerization
CN111943974B (en) Metal complex, preparation method and application thereof
Tao et al. Achiral C s-Symmetric Half-Sandwich Scandium (III) Complexes with Imine–Cyclopentadienyl Ligands Catalyze Isotactic Polymerization of 1-Hexene
CN101824053B (en) Bis-silicon-bridged dinuclear metallocene compound and preparation and application thereof
CN1551889A (en) Transition metal catalysts for olefin polymerization
CN102093494B (en) Metal olefin polymerization catalyst containing 8-hydroxyquinoline imine ligand and preparation method thereof
CN102190749B (en) Copolymerization method of ethane/alpha-alkene
CN101638422B (en) Bis-silicon-bridged metallocene compound, preparation method and application thereof
CN101638447B (en) Supported bis-silicon-bridged metallocene catalyst, preparation method and application thereof
CN102190687B (en) Constrained geometry carbon-bridged single metallocene compound, its preparation and application
Cheng et al. Ethylene polymerization using silica-supported zirconocene dibromide/methylalumoxane catalysts
CN100556910C (en) Bibridge binucleus cyclopentadienyl metal compound and its production and application
JP2004530653A (en) Non-metallocenes, their preparation and use in the polymerization of olefins
CN103288987B (en) A kind of loaded catalyst for olefinic polymerization and Synthesis and applications thereof
CN1428355A (en) Binuclear metallocene compound and its preparation and application in olefinic polymerization
CN101268106A (en) Process for the preparation of a metal-organic compound comprising a spectator ligand
CN1208339C (en) Single metallocene catalyst with naphthalene ring ligand and its prepn
CN1132855C (en) Olefine polymerizing semi-metallocene catalyst and its prepn. and application

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant