CN103772545B - Bridged cyclopentadienyl bimetallic catalyst and application thereof - Google Patents
Bridged cyclopentadienyl bimetallic catalyst and application thereof Download PDFInfo
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- CN103772545B CN103772545B CN201210405511.2A CN201210405511A CN103772545B CN 103772545 B CN103772545 B CN 103772545B CN 201210405511 A CN201210405511 A CN 201210405511A CN 103772545 B CN103772545 B CN 103772545B
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- bridged rings
- rings pentadienyl
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- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 title claims abstract description 7
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 title abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 18
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- 125000005234 alkyl aluminium group Chemical group 0.000 claims abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 6
- 125000005843 halogen group Chemical group 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 229910000078 germane Chemical group 0.000 claims abstract description 3
- -1 pentadienyl Chemical group 0.000 claims description 56
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 239000004698 Polyethylene Substances 0.000 claims description 30
- 229920000573 polyethylene Polymers 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000001291 vacuum drying Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims description 4
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical group CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 3
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical class C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 125000001118 alkylidene group Chemical group 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 18
- 239000005977 Ethylene Substances 0.000 abstract description 18
- 238000009826 distribution Methods 0.000 abstract description 10
- 230000002902 bimodal effect Effects 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 125000002947 alkylene group Chemical group 0.000 abstract 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 abstract 1
- 229920013716 polyethylene resin Polymers 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000006073 displacement reaction Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 229910010068 TiCl2 Inorganic materials 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910007928 ZrCl2 Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910007935 ZrBr2 Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- AUZMWGNTACEWDV-UHFFFAOYSA-L titanium(2+);dibromide Chemical compound Br[Ti]Br AUZMWGNTACEWDV-UHFFFAOYSA-L 0.000 description 2
- NMFOOIYPNIYAID-UHFFFAOYSA-N 6-methylidene-1-phenylcyclohexa-1,3-diene Chemical group C=C1CC=CC=C1C1=CC=CC=C1 NMFOOIYPNIYAID-UHFFFAOYSA-N 0.000 description 1
- WSNMPAVSZJSIMT-UHFFFAOYSA-N COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 Chemical compound COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 WSNMPAVSZJSIMT-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- QOXHZZQZTIGPEV-UHFFFAOYSA-K cyclopenta-1,3-diene;titanium(4+);trichloride Chemical compound Cl[Ti+](Cl)Cl.C=1C=C[CH-]C=1 QOXHZZQZTIGPEV-UHFFFAOYSA-K 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to a bridged cyclopentadienyl bimetallic catalyst and application thereof; the structural formula of the main catalyst is as follows:wherein M = Ti, Zr, or Hf; x = Cl or Br; rn = 1-3H or 1-3 Me; a. the1、A2Is identical or different and is an alkylene, silyl, siloxane or germane group; r1、R2Are identical or different radicals, and are substituted cyclopentadienyl or halogen atoms; and (3) a cocatalyst: alkyl aluminoxane or alkyl aluminum, wherein the molar ratio of the cocatalyst to the main catalyst, namely Al/M, is 200-10000: 1; the catalytic system shows the characteristic of active center diversification in catalytic polymerization reaction, and the polyethylene resin obtained by catalyzing ethylene polymerization has wide molecular weight distribution and even bimodal distribution; good stability, large adjustable range of structure and unique performance of the obtained polymer.
Description
Technical field
The present invention relates to a kind of catalyst preparing wide/double peak polyethylene, specially bridged rings pentadienyl bimetallic urge
Change and application.
Background technology
The machinability of polyvinyl resin is conflicting with mechanical strength performance, improves molecular weight and product can be made to have more preferably
Mechanical property, but simultaneously resin becomes difficult to again processing, and wide/double peak polyethylene then can solve this problem well.
Wherein vinyl polymer amount part is in order to ensure physical mechanics intensity, and low molecular weight part is in order to improve processing characteristics, wide
Molecular weight distribution makes its resisting environmental stress and cracking, croop property be strengthened, thus wide/double peak polyethylene intensity, stability,
The aspects such as low-shrinkage, splitting resistance, processing characteristics have the irreplaceable advantage of other products.
The method preparing wide/double peak polyethylene mainly has melt blend, tandem reactor method and single reactor method.Pass through
The melt blended realization of different molecular weight resin the most uniformly mixes extremely difficult, is difficult to obtain the product that performance is homogeneous.Series connection
Reaction method is relatively costly.Single reactor is also referred to as one section of reaction method, is in a reactor, by using identical or different kind
The resin of the Catalyst Production width molecular weight distribution of class.The method need not transform existing process units greatly even do not change
Make, easily implement, resin grade adjustable extent is big, cost is relatively low, and high low-molecular weight polymer mix homogeneously, be produce wide/bis-
The important research direction of peak polyethylene technology and development trend.Single reactor method includes again using the homogeneous of two or more independence
Or heterogeneous catalysis mixing method (CN03137600.2；CN200510066036.0；CN200710070353.9；
CN200910243765.7), supported catalyst method (WO9747682；CN200124701.8；Petrochemical industry, 2005,34
: 1050) and the single catalyst method of double (many) caryogamy compounds (11).
Single catalyst avoids the interaction between different catalysts and interference, it is possible to achieve catalyst catalytic performance
Stable, the purpose of products obtained therefrom stay in grade.Imines bimetallic such as the late transition metal of CN200910100768.5 announcement is different
Caryogamy compound, the Bibridge binucleus cyclopentadienyl metal compound of CN200510028619.4,4,4 '-two (methylene) biphenyl bridging dinuclear metallocene
Titanium (zirconium) compound (journal of Zhejiang university (Edition), 2006,33 (1): 76), Gorl report with salicylaldiminato
The Asymmetric Metallocene coordination compound (J organometal Chem, 2007,692:5727) of three core zirconiums of part and cyclopentadienyl ligand,
The methyl of the synthesis such as Alt and phenyl replace the asymmetric dual-core-ansa-zirconium metallocene complex (Inorg of bridging silicon atom
Chim Acta, 2003, (350): 1), the Novel asymmetric Binuclear Ti half metallocene of the 3-oxygen-pentamethylene bridging of sun research
[(CpTiC12)2(η5-C9H6(CH2CH2OCH2CH2)2η5-C5H3CH3)] (catalCommun, 2007, (8): 2025) catalysis second
Alkene is polymerized the molecular weight of polyethylene wider distribution obtained.The single catalyst of double (many) caryogamy compounds contains two or more metal
Center, though owing to the kind of metal center is different or belongs to one species but its residing chemical environment difference, thus there is difference
Catalysis characteristics, catalyzed ethylene can obtain wide/double peak polyethylene.This method products obtained therefrom stay in grade, and at single reaction
Device is polymerized, and reduces reactor quantity in technical process, reduces industrial cost, resin can be made to reach the mixing of molecular level, be
Produce important research direction and the development trend of wide/double peak polyethylene technology.Additionally, metallocene catalyst has copolymerized ability
By force, the feature that adjustability of structure is strong.But it is harsh to there is preparation condition in most metallocene catalysts, wayward in technique, heat
The problems such as stability is the most poor.
Summary of the invention
It is an object of the invention to for single reactor polyethylene device, a kind of bridged rings pentadienyl bimetallic catalytic of preparation
Agent system, utilizes the synergism of two metals in bimetallic catalyst, shows active center many in catalytic polymerization
The characteristic of sample, such that it is able to catalyzed ethylene polymerization prepares molecular weight distribution the width even polyvinyl resin of bimodal distribution.Separately
On the one hand, this type of bimetallic catalyst good stability, in atmosphere place several hours without occurring significantly to decompose, structure
Adjustable extent is big, and resulting polymers has the advantages such as special performance, beneficially commercial Application.
The technical solution adopted in the present invention is:
The bridged rings pentadienyl bimetallic catalyst system of synthesis wide/double peak polyethylene, it is characterised in that under it includes
State composition:
Major catalyst: bridged rings pentadienyl bimetallic catalyst, structural formula is as follows:
Wherein M=Ti, Zr or Hf；X=Cl or Br；Rn=1～3H or 1～3Me；A1、A2For identical or different abutment, it is sub-
Alkyl, silylation, siloxy group or germane base；R1、R2It is identical or different group, former for substituted cyclopentadienyl group, halogen
Son.
Promoter: alkylaluminoxane or alkyl aluminum.The bridged rings pentadienyl of described synthesis wide/double peak polyethylene is double
Metallic catalyst, it is characterised in that promoter aluminium alkyl oxygen alkane be MAO (MAO), ethylaluminoxane (EAO) or
Modified methylaluminoxane (MMAO), alkyl aluminum is AlEt3、Al(i-Bu)3, promoter with mol ratio Al/M of major catalyst is
500～8000:1.
The bridged rings pentadienyl bimetallic catalyst of above-mentioned synthesis wide/double peak polyethylene, it is characterised in that abutment A1、
A2For identical or different group, it is Me2C、CH2CH2、Me2Si、Me2SiSiMe2、Me2SiOSiMe2、Me2Ge。
The bridged rings pentadienyl bimetallic catalyst of above-mentioned synthesis wide/double peak polyethylene, it is characterised in that R1、R2It is
Identical or different group, is H, CH for substituent group3、CH3CH2、(CH3)2CH2Cyclopentadienyl group；Halogen atom.
The synthetic method of the bridged rings pentadienyl bimetallic catalyst of above-mentioned synthesis wide/double peak polyethylene is as follows:
In reaction bulb after evacuated argon is replaced, by RCpMCl3(R=H, methyl, ethyl, isopropyl, M=Ti,
Zr, Hf) it is dissolved in THF, the most again by H2O(RCpMCl3:H2O=1.875:1) be dissolved in THF be slowly dropped to above-mentioned molten
In liquid, drip after at room temperature continuing reaction 12h, most THF is steamed, is subsequently adding a large amount of normal hexane, has solid
Separating out, filtration and recrystallization vacuum drying obtain (RCpMCl2)2O.In reaction bulb after evacuated argon is replaced, will be with
Identical or different abutment Me2C、CH2CH2、Me2Si、Me2SiSiMe2、Me2SiOSiMe2、Me2The doube bridge chain of rings pentadiene of Ge is dissolved in
Normal hexane, is slowly added dropwise the hexane solution (n-BuLi: doube bridge chain of rings pentadiene=2:1) of n-BuLi, drips complete, slowly at 0 DEG C
It is warmed to room temperature reaction 6 hours, obtains suspension, leach the supernatant, add THF after draining solvent, then add above-mentioned at 0 DEG C
(the RCpMCl that method obtains2)2O(doube bridge chain of rings pentadiene: (RCpMCl2)2O=1:1), after 12h is stirred at room temperature, pump solvent,
Residue CH2Cl2Extract, gained clear filtrate concentrating under reduced pressure, add appropriate amount normal hexane, freezing, filter precipitation dried
Obtain the bridged rings pentadienyl bimetallic catalyst such as structure I, such as (Me2C)2(C5H3)2(CpTiCl)2O、
(Me2SiOSiMe2)2(C5H3)2(CpHfCl)2O、(Me2C)(Me2Si)(C5H3)2(CpZrCl)2O、(Me2Ge)2(2-MeC5H2)2
(EtCpTiCl)2O。
The bridged rings pentadienyl bimetallic catalyst of structure I is dissolved in THF, and ice-water bath cooling is lower adds concentrated hydrochloric acid or dense
HBr(HX:I=40:1), continuation reaction then it is warmed to room temperature overnight.Decompressing and extracting solvent, residue CH2Cl2Extract, filter,
Filtrate adds appropriate amount normal hexane after concentrating, freezing, must be such as the bridged rings pentadienyl of structure II after filtering precipitation vacuum drying
Bimetallic catalyst, such as (Me2Si)(Me2C)(C5H3)2(CpZrCl)O(ZrCl2)、(Me2SiOSiMe2)2(C5H3)2(CpTiCl)
O(TiCl2)、(Me2C)(Me2Si)(C5H3)2(CpZrBr)O(ZrBr2)、(Me2SiSiMe2)2(2-EtC5H2)2(EtCpTiCl)O
(EtCpTiCl2)。
In reaction bulb after evacuated argon is replaced, will be with identical or different abutment Me2C、CH2CH2、Me2Si、
Me2SiSiMe2、Me2SiOSiMe2、Me2The doube bridge chain of rings pentadiene of Ge is dissolved in CH2Cl2, at 0 DEG C, it is slowly added dropwise the own of n-BuLi
Alkane solution (n-BuLi: doube bridge chain of rings pentadiene=2:1), drips complete, is slowly increased to room temperature reaction 2 hours, obtains suspension.
Containing MX4(MX4: doube bridge chain of rings pentadiene=2:1, X=Cl, Br, M=Ti, Zr, Hf) it is dissolved in CH2Cl2In, it is slowly added dropwise at 0 DEG C
Above-mentioned suspension, room temperature reaction 12h.Add aniline (MX4: aniline=2.5:1) and water (aniline: water=2:1), room temperature reaction 12h
Rear filtration, the normal hexane washing of the solid after evaporation solvent is dried, and obtains the bridged rings pentadienyl bimetallic such as structure III and urges
Agent, such as (Me2Si)2(C5H3)2(TiCl2)2O、(Me2SiOSiMe2)2(C5H3)2(HfCl2)2O、(Me2C)(Me2Si)(C5H3)2
(ZrBr2)2O、(Me2SiSiMe2)(Me2SiOSiMe2)(3-MeC5H2)2(TiCl2)2O。
The purposes of the bridged rings pentadienyl bimetallic catalyst system of above-mentioned synthesis wide/double peak polyethylene is main catalytic
Agent carries out catalyzed ethylene polymerization under the effect of promoter.Its concrete polymerization technique is: fill for three times to through nitrogen displacement again
Enter in the reaction vessel of ethylene, add the toluene gone out through metallic sodium cohobation that volume is reaction vessel 1/5th, polymerization
Pressure 0.1～5MPa, reaction temperature 0～100 DEG C, by formula proportion be separately added into major catalyst (major catalyst concentration is 1 ×
10-5～1 × 10-3Mol/L), promoter, polyreaction starts, and polymerization time is 0.5～4 hour, is subsequently adding volume hundred
Point concentration is the concentrated hydrochloric acid acidic ethanol of 10%, makes reaction terminating, with water, washing with alcohol, filtered polymeric, then in 70 DEG C of vacuum
Drying baker is dried 8 hours, obtains product polyethylene.This catalyst activity is 1 × 104～1 × 107GPE/mol h, poly-
The molecular weight distribution width of ethylene or in bimodal distribution.
Detailed description of the invention
Embodiment 1
Evacuated argon replace after 250ml reaction bulb in, by 6.52g(30mmol) CpTiCl3It is dissolved into
In 200mlTHF, the most again by 0.28g(16mmol) water dissolution in the THF of 40ml, and be slowly dropped in above-mentioned solution,
Drip after at room temperature continuing reaction 12h, most THF steamed, is subsequently adding a large amount of normal hexane, have solid to separate out,
Filter, then obtain (CpTiCl with carbon tetrachloride recrystallization vacuum drying2)2O4.25g, productivity 75%.Put at evacuated argon
In 250ml reaction bulb after changing, by 1.05g(5mmol) (Me2C)2(C5H3)2It is dissolved in 50ml normal hexane, is slowly added dropwise at 0 DEG C
The hexane solution of 10mmol n-BuLi, drips complete, is slowly increased to room temperature reaction 6 hours, obtains white suspension, leaches
Layer clear liquid, drains solvent, adds 60mlTHF, then add 1.91g(5mmol at 0 DEG C) (CpTiCl2)2O, is stirred at room temperature
After 12h, pump solvent, residue CH2Cl2Extract, gained clear filtrate concentrating under reduced pressure, add appropriate amount normal hexane, cold
Freeze, filter precipitation and obtain (Me after drying2C)2(C5H3)2(CpTiCl)2O 1.57g, productivity 60%.Elementary analysis measured value: C,
59.3%;H,5.1%。
It is re-filled with for three times in the 250ml reactor of ethylene adding what 50ml went out through metallic sodium cohobation to through nitrogen displacement
Toluene, stirring is warmed up to 30 DEG C, is passed through in ethylene makes reactor and keeps pressure 0.1MPa, is separately added into major catalyst (Me2C)2
(C5H3)2(CpTiCl)2O(concentration is 1 × 10-5Mol/L), promoter MAO(Al/Ti mol ratio be 500:1), polymerization time
Being 2 hours, (i.e. volume ratio is 37% concentrated hydrochloric acid: anhydrous second to be subsequently adding the acidic ethanol that 10ml concentration expressed in percentage by volume is 10%
Alcohol=1:9) to reaction terminating, with water, washing with alcohol, filtered polymeric, then it is dried 8 hours in 70 DEG C of vacuum drying ovens, obtains
Product polyethylene.Its activity is 7.9 × 104GPE/mol h, polyethylene fusing point is 131.2 DEG C, Mw(weight average molecular weight) be
63.6×104G/mol, MWD(molecular weight distribution) be that 7.3(GPC records).
Embodiment 2
By 0.507g(1mmol) (Me2Si)(Me2C)(C5H3)2(CpZrCl)2O is dissolved in 30mlTHF, under ice-water bath cooling
Add 3ml(12M, 40mmol) concentrated hydrochloric acid, then it is warmed to room temperature continuation reaction overnight.Decompressing and extracting solvent, residue CH2Cl2
Extract, filter, after filtrate concentration, add appropriate amount normal hexane, freezing, filter after precipitation vacuum is drained and obtain (Me2Si)(Me2C)
(C5H3)2(CpZrCl)O(ZrCl2) 0.59g, productivity 90%.Elementary analysis measured value: C, 40.7%;H,3.9%.
It is re-filled with for three times in the 250ml reactor of ethylene adding what 50ml went out through metallic sodium cohobation to through nitrogen displacement
Toluene, stirring is warmed up to 0 DEG C, is passed through in ethylene makes reactor and keeps pressure 2MPa, is separately added into major catalyst (Me2Si)
(Me2C)(C5H3)2(CpZrCl)O(ZrCl2) (concentration is 9 × 10-4Mol/L), promoter EAO(Al/Zr mol ratio is
2000:1), polymerization time is 0.5 hour, is subsequently adding acidic ethanol that 10ml concentration expressed in percentage by volume is 10% to reaction terminating,
With water, washing with alcohol, filtered polymeric, then it is dried 8 hours in 70 DEG C of vacuum drying ovens, obtains product polyethylene.Its activity
It is 9.0 × 105GPE/mol h, polyethylene fusing point is 128.2 DEG C, and Mw is 37.0 × 104G/mol, MWD=6.0.
Embodiment 3
According to the method described in embodiment 1, by 10.5g(30mmol) CpHfCl3With 0.28g(16mmol) water react
Obtain (CpHfCl2)2O 6.9g, productivity 72%.Again by 1.95g(5mmol) (Me2SiOSiMe2)2(C5H3)2With 4.72g
(5mmol) (CpHfCl2)2O reaction obtains (Me2SiOSiMe2)2(C5H3)2(CpHfCl)2O 2.42g, productivity 50%.Element divides
Analysis measured value: C, 35.0%;H, 4.3%.
It is re-filled with for three times in the 250ml reactor of ethylene adding what 50ml went out through metallic sodium cohobation to through nitrogen displacement
Toluene, stirring is warmed up to 90 DEG C, is passed through in ethylene makes reactor and keeps pressure 3.5MPa, is separately added into major catalyst
(Me2SiOSiMe2)2(C5H3)2(CpHfCl)2O(concentration is 2 × 10-4Mol/L), promoter MMAO(Al/Hf mol ratio is
4000:1), polymerization time is 1 hour, is subsequently adding acidic ethanol that 10ml concentration expressed in percentage by volume is 10% to reaction terminating, uses
Water, washing with alcohol, filtered polymeric, then be dried 8 hours in 70 DEG C of vacuum drying ovens, obtain product polyethylene.Its activity is
8.5×106GPE/mol h, polyethylene fusing point is 129.7 DEG C, and Mw is 9.5 × 104G/mol, MWD=5.7.
Embodiment 4
According to the method described in embodiment 1, by CpTiCl3(the CpTiCl obtained is reacted with water2)2O and (Me2SiSiMe2)2
(C5H3)2Reaction, obtains (Me2SiSiMe2)2(C5H3)2(CpTiCl)2O.By 0.67g(1mmol) (Me2SiSiMe2)2(C5H3)2
(CpTiCl)2O is dissolved in 30mlTHF, adds 5.7ml(7M, 40mmol under ice-water bath cooling) dense HBr, then it is warmed to room temperature and continues
Continuous reaction is overnight.Decompressing and extracting solvent, residue CH2Cl2Extracting, filter, filtrate adds appropriate amount normal hexane after concentrating, cold
Freeze, filter after precipitation vacuum is drained and obtain (Me2SiSiMe2)2(C5H3)2(CpTiBr)O(TiBr2) 0.34g, productivity 45%.Element divides
Analysis measured value: C, 35.1%;H,4.2%.
It is re-filled with for three times in the 250ml reactor of ethylene adding what 50ml went out through metallic sodium cohobation to through nitrogen displacement
Toluene, stirring is warmed up to 20 DEG C, is passed through in ethylene makes reactor and keeps pressure 4.8MPa, is separately added into major catalyst
(Me2SiSiMe2)2(C5H3)2(CpTiBr)O(TiBr2) (concentration is 5 × 10-4Mol/L), promoter MAO(Al/Ti mol ratio
For 6000:1), polymerization time is 4 hours, is subsequently adding acidic ethanol that 10ml concentration expressed in percentage by volume is 10% to reaction terminating,
With water, washing with alcohol, filtered polymeric, then it is dried 8 hours in 70 DEG C of vacuum drying ovens, obtains product polyethylene.Its activity
It is 7.1 × 106GPE/mol h, polyethylene fusing point is 131.2 DEG C, and Mw is 43.1 × 104G/mol, MWD=7.4(are bimodal).
Embodiment 5
Evacuated argon replace after 250ml reaction bulb in, by 1.21g(5mmol) (Me2Si)2(C5H3)2It is dissolved in
20ml CH2Cl2, it is slowly added dropwise the hexane solution of 10mmol n-BuLi at 0 DEG C, drips complete, be slowly increased to room temperature reaction 2 little
Time, obtain suspension.Containing 1.89g(10mmol) TiCl4It is dissolved in 5mlCH2Cl2In, at 0 DEG C, it is slowly added dropwise above-mentioned suspension,
Room temperature reaction 12h.Add 4.4ml(4mmol) aniline and 0.036g(2mmol) water, filter after room temperature reaction 12h, evaporate molten
Solid after agent normal hexane washs, and obtains (Me2Si)2(C5H3)2(TiCl2)2O 0.59g, productivity 60%.Elementary analysis is surveyed
Value: C, 33.4%;H,3.5%.
It is re-filled with for three times in the 250ml reactor of ethylene adding what 50ml went out through metallic sodium cohobation to through nitrogen displacement
Toluene, stirring is warmed up to 20 DEG C, is passed through in ethylene makes reactor and keeps pressure 4.8MPa, is separately added into major catalyst (Me2Si)2
(C5H3)2(TiCl2)2O(concentration is 5 × 10-4Mol/L), promoter AlEt3(Al/Ti mol ratio is 2000:1), polymerization time
It is 4 hours, is subsequently adding acidic ethanol that 10ml concentration expressed in percentage by volume is 10% to reaction terminating, with water, washing with alcohol, filtration
Polymer, then be dried 8 hours in 70 DEG C of vacuum drying ovens, obtain product polyethylene.Its activity is 5.8 × 105gPE/mol·
H, polyethylene fusing point is 130.5 DEG C, and Mw is 5.6 × 104G/mol, MWD=11.8(are bimodal).
Embodiment 6
According to the method described in embodiment 1, by 11.4g(30mmol) EtCpTiBr3With 0.28g(16mmol) water anti-
(EtCpTiBr should be obtained2)2O 6.4g, productivity 65%.Again by 1.80g(5mmol) (Me2Ge)2(2-MeC5H2)2With 3.1g
(5mmol) (EtCpTiBr2)2O reaction obtains (Me2Ge)2(2-MeC5H2)2(EtCpTiBr)2O 1.46g, productivity 40%.Element
Analysis measured value: C, 39.5%;H,3.5%.
It is re-filled with for three times in the 250ml reactor of ethylene adding what 50ml went out through metallic sodium cohobation to through nitrogen displacement
Toluene, stirring is warmed up to 90 DEG C, is passed through in ethylene makes reactor and keeps pressure 1.0MPa, is separately added into major catalyst (Me2Ge)2
(2-MeC5H2)2(EtCpTiBr)2O(concentration is 5 × 10-5Mol/L), promoter Al (i-Bu)3(Al/Ti mol ratio is
8000:1), polymerization time is 2.5 hours, is subsequently adding acidic ethanol that 10ml concentration expressed in percentage by volume is 10% to reaction terminating,
With water, washing with alcohol, filtered polymeric, then it is dried 8 hours in 70 DEG C of vacuum drying ovens, obtains product polyethylene.Its activity
It is 5.4 × 104GPE/mol h, polyethylene fusing point is 132.0 DEG C, and Mw is 26.3 × 104G/mol, MWD=10.3(are bimodal).
Claims (5)
1. a bridged rings pentadienyl bimetallic catalyst, it is characterised in that it includes following composition:
Major catalyst: bridged rings pentadienyl bimetallic catalyst, structural formula is as follows:
Wherein M=Ti, Zr or Hf；X=Cl or Br；Rn=1～3Me；A1、A2For identical or different abutment, it is alkylidene, silicon
Alkyl, siloxy group or germane base；R1、R2It is identical or different group, for substituted cyclopentadienyl group, halogen atom；
Promoter: alkylaluminoxane or alkyl aluminum, promoter is 200～10000 with the mol ratio i.e. Al/M of major catalyst:
1。
Bridged rings pentadienyl bimetallic catalyst the most according to claim 1, it is characterised in that promoter alkyl aluminum
Oxygen alkane is MAO, ethylaluminoxane or modified methylaluminoxane, and alkyl aluminum is AlEt3、Al(i-Bu)3, promoter
It is 500～8000:1 with mol ratio Al/Ti of major catalyst.
Bridged rings pentadienyl bimetallic catalyst the most according to claim 1, it is characterised in that abutment A1、A2For identical
Or different groups, it is Me2C、CH2CH2、Me2Si、Me2SiSiMe2、Me2SiOSiMe2Or Me2Ge。
Bridged rings pentadienyl bimetallic catalyst the most according to claim 1, it is characterised in that R1、R2It is identical or not
Same group, is H, CH for substituent group3、CH3CH2、(CH3)2The cyclopentadienyl group of CH；Halogen atom.
5. the purposes of the bridged rings pentadienyl bimetallic catalyst described in a claim 1；It is characterized in that, be main catalytic
Wide/double peak polyethylene is prepared in agent polymerization under the effect of promoter, and major catalyst concentration is 1 × 10-5～1 × 10-3mol/L；
Its polymerization temperature is 0～100 DEG C, and polymerization pressure is 0.1～5MPa, and polymerization time is 0.5～4h, is subsequently adding volume basis dense
Degree is the concentrated hydrochloric acid acidic ethanol of 10%, makes reaction terminating, with water, industrial alcohol washing, filtered polymeric, then in 70 DEG C of vacuum
Drying baker is dried 8 hours, obtains product polyethylene.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1276386A (en) * | 2000-06-22 | 2000-12-13 | 中国石油化工集团公司 | silicobridged binuclear metallocene zirconium compound |
| CN101392036A (en) * | 2008-11-05 | 2009-03-25 | 河北工业大学 | Metallocene domino catalytic system for preparing branched polyethylene using ethylene as only monomer and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1276386A (en) * | 2000-06-22 | 2000-12-13 | 中国石油化工集团公司 | silicobridged binuclear metallocene zirconium compound |
| CN101392036A (en) * | 2008-11-05 | 2009-03-25 | 河北工业大学 | Metallocene domino catalytic system for preparing branched polyethylene using ethylene as only monomer and use thereof |
Non-Patent Citations (2)
| Title |
|---|
| Shuang Luo et al..Synthesis, Structures, and Polymerization Catalytic Properties of doubly Bridged Bis(cyclopentadienyl) Dinuclear (μ-Oxo)titanium Complexes.《Organometallics》.2009,第28卷(第10期), * |
| 朱柏林等.双桥连二环戊二烯基金属有机化合物的研究进展.《有机化学》.2003,第23卷(第10期), * |
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