CN100556910C - Bibridge binucleus cyclopentadienyl metal compound and its production and application - Google Patents
Bibridge binucleus cyclopentadienyl metal compound and its production and application Download PDFInfo
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- CN100556910C CN100556910C CNB2005100286194A CN200510028619A CN100556910C CN 100556910 C CN100556910 C CN 100556910C CN B2005100286194 A CNB2005100286194 A CN B2005100286194A CN 200510028619 A CN200510028619 A CN 200510028619A CN 100556910 C CN100556910 C CN 100556910C
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Abstract
The invention discloses a kind of Bibridge binucleus cyclopentadienyl metal compound and preparation method thereof and in olefinic polymerization, use.The preparation method comprises the steps: ligand L and RCpMCl
3Target product is collected in reaction then from reaction product.Restriction configuration Bibridge binucleus cyclopentadienyl metal compound of the present invention can be used as catalyzer, be used for the alhpa olefin copolymerization, the advantage of restriction configuration Bibridge binucleus cyclopentadienyl metal compound of the present invention is fairly obvious: synthetic route is simple, the product yield height, separation and purification is easy, needs promotor few, the catalytic activity height, polyolefin molecular weight distributes wide, collateralization degree height.The polyethylene of catalysis gained is measured by GPC has wide molecular weight distribution or bimodal distribution (MWD=26.6), and collateralization passes through
13C-NMR measures, and product has good processing properties, satisfies industrial needs, has a wide range of applications.
Description
Technical field
The present invention relates to a kind of alhpa olefin catalyst for copolymerization, relate in particular to a kind of Bibridge binucleus cyclopentadienyl metal compound.
Background technology
The fifties in last century, the discovery of ferrocene and Ziegler-Natta (G.Natta; P.Ginnini, J.Am.Chem.Soc., 1954,79:2975) catalyzer is applied to ethene, propylene polymerization, has made Organometallic Chemistry obtain fast development, since 1960, a large amount of novel metal organic compound are successfully synthesized, 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 people such as Kaminsky (W.Kaminsky, M.Miri, H.Sinn, R.Woldt, Makromol.Common., 1983,4:417) find methylaluminoxane (MAO) and Cp
2ZrMe
2The catalyst system of forming is dissolvable in water in the toluene, homogeneous phase highly active catalytic vinyl polymerization, and activity reaches 40,000kgPE/g.Zr.h, this discovery has greatly shaken industry member at that time.Now, the polyolefine annual production 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 single center and multicenter two classes, and the monokaryon metallocene catalyst is the emphasis of various countries scientist research always, has almost been covered all respects of this research field by the monokaryon catalyzer of patent protection.But also there is the high defective of using dosage in present catalyzer, and the promotor of high dosage is a big bottleneck of restriction metallocene catalyst industrial application.
The research prospect of restriction configuration Bibridge binucleus cyclopentadienyl metal is very good, and this area research is very active in recent years.The contriver has carried out long term studies to the preparation and the application of restriction configuration Bibridge binucleus cyclopentadienyl metal, the imines double-core compounds that successfully synthetic a series of aryl replaces, and applied for that (Chinese patent application number: 99124191.6,01144963.2), its activity reaches 10 to patent
5GPE/mol.Ti.h.
The compound of the titanium of similar structures has the bibliographical information mistake:
[Joyce Y.Corey, Jean L.Huhmann, Nigam P.Rath, Inorg.Chem., 1995,34:3203-3209], the compound of similar part trichlorine titanium also has the people to synthesize [Ana Cano, Tom á s Cuenca, Pilar G ó mez-sal, BeatrizRoyo, Pascual Royo, Organometallics, 1994,13:1688-1694], 1996, people such as Jean L.Huhmann report [Jean L.Huhmann, Joyce Y.Corey, Nigam P.Rath, Organometallics 1996,15 (19): 4063-4074] asymmetric double silicon-bridged dinuclear complex compound is not all seen the report of relevant olefinic polymerization.First relevant this compounds is applied to the example of olefinic polymerization by Lang report [Heinrich Lang, Sabine Blau, Andreas Much, Karin Weiss, Ute Neugebauer, J.Organomet.Chem., 1995,490:C32-C36], when 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.King one hundred congruent people [Shansheng Xu, XuliangDai, Tao Wu, Baiquan Wang, Xiuzhong Zhou, Linhong Weng, J.Organomet.Chem., 2002,645:212] the synthetic pair different bridge binuclear compounds that mix, a bridge is a carbon, and another is silicon or germanium, the vinyl polymerization result: 0.5 hour reaction times, vinyl monomer pressure 100kPa, MAO:Al=2500, M=Zr, 40 ℃ of polymerization temperatures, activity are 3.94 * 10
6GPE/mol.Zr.h.But about the synthetic of the compound of the zirconium hafnium of structural similitude with use report is never arranged.
The catalyzer that above-mentioned document relates to, the preparation route is long, and product yield is low, needs promotor ratio height.
Along with science and technology development, people make every effort to that the development research activity is higher, and cost is lower, and purposes is the Bibridge binucleus cyclopentadienyl metal catalyzer more widely, to satisfy the needs that polyolefin industry is produced.
Summary of the invention
One of the object of the invention is to disclose a kind of Bibridge binucleus cyclopentadienyl metal compound, to overcome the defective that prior art exists.
Two of the object of the invention is the preparation method of open Bibridge binucleus cyclopentadienyl metal compound.
Three of the object of the invention is that open Bibridge binucleus cyclopentadienyl metal compound is as the application of catalyzer in olefinic polymerization.
Technical conceive of the present invention:
Studies show that restriction configuration Bibridge binucleus cyclopentadienyl metal catalyzer owing to produce two centers synergy, as introduce different substituents on luxuriant ring, can effectively improve catalyst performance, test-results proves that the promotor ratio greatly reduces.The structure of the said restriction configuration of the present invention Bibridge binucleus cyclopentadienyl metal compound is as follows:
Wherein:
M represents Ti, Zr or Hf;
R represents hydrogen, alkyl, aryl, thiazolinyl or alkoxyl group;
Preferred R is alkyl, C3～C10 thiazolinyl or the C3～C6 alkoxyl group of C1～C10, and preferred aryl groups is the alkyl that contains phenyl ring;
Preferred R be C1～C4 alkyl, C3～C4 thiazolinyl or C3～C5 alkoxyl group;
Most preferred R is methyl, sec.-propyl or butyl, and most preferred aryl is a benzyl;
Preferred compound is:
[MeCpTiCl
2]
2[μ，μ-(Me
2Si)
2(C
5H
3)
2]、
[i-PrCpTiCl
2]
2[μ，μ-(Me
2Si)
2(C
5H
3)
2]、
[n-BuCpTiCl
2]
2[μ，μ-(Me
2Si)
2(C
5H
3)
2]、
[HC＝CHCH
2CpTiCl
2]
2[μ，μ-(Me
2Si)
2(C
5H
3)
2]、
[BezylCpTiCl
2]
2[μ，μ-(Me
2Si)
2(C
5H
3)
2]、
[CpZrCl
2]
2[μ，μ-(Me
2Si)
2(C
5H
3)
2]、
[MeCpZrCl
2]
2[μ，μ-(Me
2Si)
2(C
5H
3)
2]、
[n-PrCpZrCl
2]
2[μ，μ-(Me
2Si)
2(C
5H
3)
2]、
[(CH
3)
2CHCpZrCl
2]
2[μ，μ-(Me
2Si)
2(C
5H
3)
2]、
[n-BμCpZrCl2]
2[μ，μ-(Me
2Si)
2(C
5H
3)
2]、
[Ph(CH
2)
2CpZrCl
2]
2[μ，μ-(Me
2Si)
2(C
5H
3)
2]、
[HC＝CHCH
2CpZrCl
2]
2[μ，μ-(Me
2Si)
2(C
5H
3)
2]、
[HC＝CHCH
2CH
2CpZrCl
2]
2[μ，μ-(Me
2Si)
2(C
5H
3)
2]、
[BezylCpZrCl
2]
2[μ, μ-(Me
2Si)
2(C
5H
3)
2] or
[MeOCH
2CH
2CpZrCl
2]
2[μ，μ-(Me
2Si)
2(C
5H
3)
2]。
The preparation method of said restriction configuration Bibridge binucleus cyclopentadienyl metal compound of the present invention comprises the steps:
With two silicon bridge ligand L and RCpMCl
3Place solvent, react under inert atmosphere, temperature of reaction is-78～100 ℃, and optimizing temperature is that 0-25 ℃ of reaction times is 1.0～24 hours, and the optimization time is 2.0-10 hour, collects target product then from reaction product.
Wherein:
Said pair of silicon bridge ligand L structure is as follows:
Said pair of silicon bridge ligand L can adopt document [Siemeling, U.Doctoral thesis Bielefeld, Germany, 1989] disclosed method to be prepared, the document play-by-play preparation method of two silicon bridge ligand L, the present invention repeats no more;
Said RCpMCl
3Structure be in following one:
Wherein: R is same as above;
Said RCpMCl
3The preparation method in document [Organometallics9 (1990) 2426 for E.C.Lund, T.Livinghouse], open report has been arranged;
RCpMCl
3With the L ratio be 2.0～2.5, top condition is 1: 2.0～2.1;
Said solvent refers to tetrahydrofuran (THF), toluene or methylene dichloride etc.;
The compound yield is 30～90%.
Restriction configuration Bibridge binucleus cyclopentadienyl metal compound of the present invention can be used as catalyzer, is used for the alhpa olefin copolymerization, as the copolymerization of ethene, ethene/1-hexene.Compound of the present invention, the catalyst performance excellence, activity remains unchanged substantially under low promotor ratio condition, and activity still can reach 10
6GPE/mol M h, the step of polyreaction and processing condition and document [J.L.Huang, Z.F.Feng, Y.J.Xu, H.Wang, Y.L.Qian, J.Q.Sun, W.Chen, G.Zheng, J.Mol.Catal.A:Chem.189 (2002) 187] disclosed method is identical, wherein, promotor MAO (methyl alcoxyl aluminium) or B (C
6F
5)
3, with the molar ratio of compound be 50～4000.Be preferably 100～500.
The present invention is at CpMCl
3But luxuriant ring on introduce and to contain various heteroatomss and various coordinating group, a series of doube bridge binuclear cyclopentadinyl titanium, zirconium, luxuriant hafnium compound have been obtained first, yield is up to 90%, the advantage of restriction configuration Bibridge binucleus cyclopentadienyl metal compound of the present invention is fairly obvious: synthetic route is simple, the product yield height, and separation and purification is easy, need promotor few, the catalytic activity height, polyolefin molecular weight distributes wide, collateralization degree height.
The present invention adopts Bibridge binucleus cyclopentadienyl metal catalyzer/MAO or Bibridge binucleus cyclopentadienyl metal catalyzer/B (C
6F
5)
3System under low ratio promotor effect, not only obtains high reactivity to vinyl polymerization, and ethene, 1-hexene are obtained high reactivity equally.
Catalyzed ethylene polymerization and copolymerization active testing, promotor are MAO or B (C
6F
5)
3, the result is as follows:
Field of activity: 1.0 * 10
5-9 * 10
7GPE/mol.M.h, polymerization temperature 30-90 ℃, Al/M=50-2000, time 0.5-2.0 hour.The polyethylene of catalysis gained is measured by GPC has wide molecular weight distribution or bimodal distribution (MWD=26.6), and collateralization passes through
13C-NMR measures, and product has good processing properties, satisfies industrial needs, has a wide range of applications.
Embodiment
Embodiment 1
Synthetic [MeCpTiCl
2]
2[μ, μ-(Me
2Si)
2(C
5H
3)
2]
With two silicon bridge compounds [μ, μ-(Me
2Si)
2(C
5H
4)
2] 668mg (2.74mmol) is dissolved in 50mL THF, under argon shield, normal temperature Dropwise 5 .5mmol n-BuLi, reaction 1h obtains ligand L.Under-30 ℃, add 1.3154g (5.63mmol) MeCpTiCl
3, stirring reaction 24h.With THF, normal hexane washing, the vacuum removal solvent gets red solid to product respectively.Productive rate is 68%.
MeCpTiCl
3Can adopt document [Organometallics 9 (1990) 2426 for E.C.Lund, T.Livinghouse] disclosed method to be prepared.
1H?NMR：7.37(d，4H)；6.70-6.78(m，6H)；6.18(t，4H)；2.17(s，6H)；0.38(s，12H)；IR：3180w，3093w，3079w，2988w，2950w，2923w，2896w，2855w，1496m，1448m，1407w，1373m，1243m，1210m，1070w，1052m，1041w，1023w，975m，900w，845s，818vs，782s，698w，678m，645w，597w，514m；MS：636(2，M
)；601(2，M
-Cl)；566(1，M
-2Cl)；557(3，M
-CH
3Cp)；E.A.Calc.：C?48.93％；H?5.05％；Found：C?48.56％；H?5.06％
Embodiment 2
Synthetic [i-PrCpTiCl
2]
2[μ, μ-(Me
2Si)
2(C
5H
3)
2]
With two silicon bridge compounds [μ, μ-(Me
2Si)
2(C
5H
4)
2] 576mg (2.36mmol) is dissolved in 50mL THF, under argon shield, normal temperature drips 4.72mmoln-BuLi, and reaction 2h obtains ligand L.Under 0 ℃, add 1.545g (5.90mmol) (CH
3)
2CHCpTiCl
3, stirring reaction 10h.With THF, normal hexane washing, recrystallization gets the red-purple crystal to product respectively, and productive rate is 32.3%.
(CH
3)
2CHCpTiCl
3Can adopt document [Organometallics 9 (1990) 2426 for E.C.Lund, T.Livinghouse] disclosed method to be prepared.
1H?NMR：7.37(d，4H)；6.71(t，2H)；6.72(s，4H)；6.27(s，4H)；3.01-3.04(m，2H)；1.13(d，12H)；0.39(s，12H)；IR：3105w，3080m，2975m，2970m，2890w，2880w，1495m，11460m，1430m，1400w，1380m，1215m，1240m，1080w，1070m，970m，910w，930w，870m，850s，815vs，780s，680m，600w，520m；MS：692(0.2，M
)；657(1，M
-Cl)；622(1，M
-2Cl)；E.A.Calc.：C51.88％；H?5.82％；Found：C?51.96％；H?5.85％
Embodiment 3
Synthetic [n-BuCpTiCl
2]
2[μ, μ-(Me
2Si)
2(C
5H
3)
2]
With two silicon bridge compounds [μ, μ-(Me
2Si)
2(C
5H
4)
2] 1.2472mg (4.75mmol) is dissolved in 60mL THF.Under argon shield, normal temperature drips 9.50mmol n-BuLi, and reaction 1h obtains ligand L.20 ℃, add 2.8652g (10.45mmol) CH
3(CH
2)
3CpTiCl
3, reaction 5h.With THF, normal hexane washing, the vacuum removal solvent gets red microcrystalline solids to product respectively.Productive rate is 56%.
CH
3(CH
2)
3CpTiCl
3Can adopt document [Organometallics 9 (1990) 2426 for E.C.Lund, T.Livinghouse] disclosed method to be prepared.
1H?NMR：7.36(s，4H)；6.72(m，6H)；6.21(s，4H)；2.55(t，4H)；1.44-1.50(m，4H)；1.24-1.30(m，4H)；0.86(t，6H)；0.40(s，12H)；IR：3100m，3090m，3070m，2945m，2930m，2850m，1495m，1470w，1460w，1450w，1430w，1400w，1380w，1240s，1210s，1100w，1080w，1050m，960m，870m，850s，840s，810vs，780s，680m，520m；MS：720(0.2，M
)；685(0.4，M
-Cl)；650(1，M
-2Cl)；
E.A.Calc.：C?53.19％；H?6.15％；Found：C?53.21％；H?6.14％。
Embodiment 4
Synthetic [HC=CHCH
2CpTiCl
2]
2[μ, μ-(Me
2Si)
2(C
5H
3)
2]
With two silicon bridge compounds [μ, μ-(Me
2Si)
2(C
5H
4)
2] 605mg (2.48mmol) is dissolved in 50mL THF, under argon shield, normal temperature drips 4.96mmoln-BuLi, and reaction 3h obtains ligand L.40 ℃, add 1.2869g (4.96mmol) CH
2=CHCH
2CpTiCl
3, with THF, normal hexane washing, recrystallization gets red solid respectively for reaction 5h, product.Productive rate is 80%.
CH
2=CHCH
2CpTiCl
3Can adopt document [Organometallics 9 (1990) 2426 for E.C.Lund, T.Livinghouse] disclosed method to be prepared.
1H?NMR：7.39(d，4H)；6.74-6.76(m，6H)；6.22(t，4H)；5.88(m，2H)；4.99-5.05(m，4H)；3.35(d，4H)；0.39(s，12H)；IR：3098m，2954m，2924s，2853m，1638m，1494m，1462w，1427m，1409w，1379w，1242s，1211s，1080w，1052m，996w，961m，906w，859s，840vs，814vs，778s，752w，733w，695w，678m，642w，623w，588w，571w，515m；MS：688(1，M
)；653(1，M
-Cl)；618(2，M
-2Cl)；E.A.Calc.：C?52.20％；H?5.26％；Found：C?52.93％；H?5.60％。
Embodiment 5
Synthetic [PhCH
2CpTiCl
2]
2[μ, μ-(Me
2Si)
2(C
5H
3)
2]
With two silicon bridge compounds [μ, μ-(Me
2Si)
2(C
5H
4)
2] 564mg (2.31mmol) is dissolved in 50mL THF.Under argon shield, normal temperature drips 4.63mmol n-BuLi, and reaction 3h obtains ligand L.Under 30 ℃, add 1.4349gPhCH
2CpTiCl
3, with THF, normal hexane washing, recrystallization gets red microcrystalline solids respectively for reaction 5h, product.Productive rate is 90%.
PhCH
2CpTiCl
3Can adopt document [Organometallics 9 (1990) 2426 for E.C.Lund, T.Livinghouse] disclosed method to be prepared.
1H?NMR：7.43(d，4H)；7.16-7.29(m，10H)；6.76(t，4H)；6.74(t，2H)；6.30(t，4H)；3.88(s，4H)；0.42(s，12H)；IR：3110w，3080w，3025w，2920w，1720w，1600w，1480m，1460w，1450w，1420w，1400w，1370w，1250m，1215m，1080w，1060m，1035m，960m，850s，820vs，780s，705s，680m，520m；MS：788(0.1，M
)；753(0.1，M
-Cl)；718(3，M
-2Cl)；E.A.Calc.：C57.73％；H?5.11％；Found：C?57.46％；H?5.20％
Embodiment 6
Synthetic [CpZrCl
2]
2[μ, μ-(Me
2Si)
2(C
5H
3)
2]
With two silicon bridge compounds [μ, μ-(Me
2Si)
2(C
5H
4)
2] 500mg (2.00mmol), under argon shield, (1.83mol/L, 4.0mmol) reaction is spent the night ,-78 ℃ of adding 1.712g CpZrCl with 2.2mln-BuLi
3DME (5.0mmol), stirring reaction 1.0h.Drain solvent, CH
2Cl
2/ n-Hexane recrystallization obtains the white powder solid.Yield is 45%.M.p.215-220℃。
CpZrCl
3DME can adopt document [Organometallics 9 (1990) 2426 for E.C.Lund, T.Livinghouse] disclosed method to be prepared.
1HNMR δ: 7.03 (s, 4H), 6.40 (s, 10H), 6.49 (s, 2H), 0.51 (s, 12H); I.R.:3110w, 3058w, 2990w, 2940w, 2920w, 2850w, 1640w, 1490w, 1450w, 1370m, 1240m, 1160w, 1045m, 960m, 920w, 910w, 870w, 810s, 771s, 680m, 645w, 610w, 510m; M.S.:Fw=706,690 (23, M
-CH
3); E.A.: calculated value: C%=41.36; H%=4.05, measured value: C%=41.42; H%=4.51.
Embodiment 7
Synthetic [MeCpZrCl
2]
2[μ, μ-(Me
2Si)
2(C
5H
3)
2]
With two silicon bridge compounds [μ, μ-(Me
2Si)
2(C
5H
4)
2] 500mg (2.00mmol), under argon shield, and normal temperature and 2.2ml n-BuLi (1.83mol/L, 4.0mmol) reaction is spent the night and is obtained ligand L, and-78 ℃ add 1.912gCH
3CpZrCl
3DME (5.0mmol), stirring reaction 1.0h.Drain solvent, CH
2Cl
2/ n-Hexane recrystallization obtains the white powder solid.Yield is 47%.M.p.228-230℃。
CH
3CpZrCl
3DME can adopt document [Organometallics 9 (1990) 2426 for E.C.Lund, T.Livinghouse] disclosed method to be prepared.
1HNMR δ: 7.01 (d, 4H), 6.47 (t, 2H), 6.26 (t, 4H), 6.06 (t, 4H), 2.21 (s, 6H), 0.51 (s, 12H); I.R.:3112w, 3085w, 3068w, 2996w, 2949w, 2925w, 2891w, 2855w, 1644w, 1499w, 1451w, 1396w, 1373m, 1242m, 1199m, 1169w, 1081w, 1055m, 1041m, 961m, 924w, 911w, 885w, 873w, 836s, 814s, 781s, 684m, 647w, 611w, 513m; M.S.:Fw=720,705 (23, M
-CH
3); E.A.: calculated value: C%=43.07; H%=4.45, measured value: C%=42.52; H%=4.44.
Embodiment 8
Synthetic [n-PrCpZrCl
2]
2[μ, μ-(Me
2Si)
2(C
5H
3)
2]
With two silicon bridge compounds [μ, μ-(Me
2Si)
2(C
5H
4)
2] (1.83mol/L, 3.38mmol) under argon shield, spend the night and obtain ligand L by normal-temperature reaction with 1.9mLn-BuLi for 412mg (1.69mmol).-30 ℃ add 1.34gCH
3CH
2CH
2CpZrCl
3DME (3.38mmol), stirring reaction 24h drains solvent, CH
2Cl
2/ n-Hexane recrystallization obtains colourless acicular crystal.Yield 41%.M.p.226℃。
CH
3CH
2CH
2CpZrCl
3DME can adopt document [Organometallics9 (1990) 2426 for E.C.Lund, T.Livinghouse] disclosed method to be prepared.
1HNMR δ: 7.03 (d, 4H), 6.48 (t, 2H), 6,28 (t, 4H), 6.12 (t, 4H), 2.57 (t, 4H), 1.57-1.52 (m, 4H), 0.89 (t, 6H), 0.52 (s, 12H); I.R.:3383m, 3333m, 2791m, 2725m, 2599m, 2492m, 1663w, 1496w, 1455m, 1375m, 1240s, 1209s, 1184w, 1082w, 1054m, 961m, 870m, 852s, 843s, 815s, 774m, 623m, 566m; M.S.:Fw=776,761 (45, M
-CH
3); E.A.: calculated value: C%=46.13; H%=5.16, measured value: C%=45.83; H%=5.12.
Embodiment 9
Synthetic [(CH
3)
2CHCpZrCl
2]
2[μ, μ-(Me
2Si)
2(C
5H
3)
2]
With two silicon bridge compounds [μ, μ-(Me
2Si)
2(C
5H
4)
2] (1.83mol/L, 2.40mmol) under argon shield, spend the night and obtain ligand L, 20 ℃ of adding 0.95g (CH by normal-temperature reaction with 1.4mLn-BuLi for 284mg (1.16mmol)
3)
2CH CpZrCl
3DME (2.38mmol), reaction 10h drains solvent, CH
2Cl
2/ n-Hexane recrystallization obtains the white plates solid.Yield 90%.M.p.228-230℃。
(CH
3)
2CHCpZrCl
3DME can adopt document [Organometallics9 (1990) 2426 for E.C.Lund, T.Livinghouse] disclosed method to be prepared.
1HNMR δ: 7.02 (d, 4H), 6.47 (t, 2H), 6.27 (t, 4H), 6.17 (t, 4H), 3.09-3.04 (m, 2H), 1.19 (d, 12H), 0.52 (s, 12H); I.R.:3105w, 3080w, 2975w, 2960w, 2890w, 2875w, 1660m, 1500w, 1470w, 1420w, 1410w, 1380w, 1360w, 1360w, 1320w, 1240m, 1210w, 1200m, 1080w, 1070w, 910w, 930w, 850s, 820s, 780s, 680m, 605w, 520m; M.S.:Fw=776,761 (8, M
-CH
3); E.A.: calculated value: C%=46.13; H%=5.16, measured value: C%=46.14; H%=4.82.
Embodiment 10
Synthetic [n-BuCpZrCl
2]
2[μ, μ-(Me
2Si)
2(C
5H
3)
2]
With two silicon bridge compounds [μ, μ-(Me
2Si)
2(C
5H
4)
2] (1.83mol/L, 5.05mmol) under argon shield, spend the night and obtain ligand L by normal-temperature reaction with 2.8mLn-BuLi for 612mg (2.51mmol).0 ℃ adds 2.12g n-BuCpZrCl
3DME (5.2mmol) reacts 6.0h, drains solvent, CH
2Cl
2/ n-Hexane recrystallization obtains the white plates solid.Yield 35%.M.p.228-230℃。
N-BuCpZrCl
3DME can adopt document [Organometallics 9 (1990) 2426 for E.C.Lund, T.Livinghouse] disclosed method to be prepared.
1HNMR δ: 7.02 (d, 4H), 6.47 (t, 2H), 6.27 (t, 4H), 6.11 (t, 4H), 2.61 (t, 4H), 1.53-1.47 (m, 4H), 1.35-1.27 (m, 4H), 0.89 (t, 6H), 0.52 (s, 12H); I.R.:3050m, 3040m, 3020m, 2895m, 2880m, 2800m, 1445m, 1420w, 1410w, 1400w, 1380w, 1350w, 1330w, 1190s, 1200s, 1100w, 1090w, 1050m, 960m, 870m, 850s, 840s, 810s, 780s, 680m, 520m; M.S.:Fw=790,790 (8, M
), 775 (2, M
-CH
3), E.A.: calculated value: C%=47.50; H%=5.48, measured value: C%=47.27; H%=5.35.
Embodiment 11
Synthetic [Ph (CH
2)
2CpZrCl
2]
2[μ, μ-(Me
2Si)
2(C
5H
3)
2]
With two silicon bridge compounds [μ, μ-(Me
2Si)
2(C
5H
4)
2] (1.83mol/L, 3.28mmol) under argon shield, spend the night and obtain ligand L, 35 ℃ of adding 1.51gPhCH by normal-temperature reaction with 1.8mLn-BuLi for 400mg (1.64mmol)
2CH
2CpZrCl
3DME (3.28mmol) reacts 8.0h, CH
2Cl
2/ n-Hexane recrystallization obtains the white granular solid, weighing products.Yield 35%.M.p.232-233℃。
PhCH
2CH
2CpZrCl
3DME can adopt document [Organometallics9 (1990) 2426 for E.C.Lund, T.Livinghouse] disclosed method to be prepared.
1HNMR δ: 7.26-7.23 (m, 4H), 7.17 (t, 2H), 7.10 (d, 4H), 7.00 (d, 4H), 6.44 (t, 2H), 6.25 (t, 4H), 6.03 (t, 4H), 2.91 (t, 4H), 2.83 (t, 4H), 0.50 (s, 12H); I.R.:3110w, 3080w, 3050w, 2990m, 2940m, 2900w, 1640w, 1500w, 1460w, 1420w, 1405w, 1350w, 1260m, 1220m, 1200m, 1080w, 1060w, 1035w, 960m, 850s, 820s, 780s, 680m, 510m; M.S.:Fw=886,871 (2, M
-CH
3); E.A.: calculated value: C%=53.07; H%=4.86, measured value: C%=52.59; H%=4.86.
Embodiment 12
Synthetic [HC=CHCH
2CpZrCl
2]
2[μ, μ-(Me
2Si)
2(C
5H
3)
2]
With two silicon bridge compounds [μ, μ-(Me
2Si)
2(C
5H
4)
2] 500mg (2.00mmol) and 4.2mmol n-BuLi (1.83M) are under argon shield, normal-temperature reaction 2h obtains ligand L, and 50 ℃ add 1.618gCH
2=CHCH
2CpZrCl
3DME (4.128mmol) reacts 5.0h.CH
2Cl
2/ n-Hexane recrystallization obtains white solid.Yield is 47%.
CH
2=CHCH
2CpZrCl
3DME adopts document [Organometallics9 (1990) 2426 for E.C.Lund, T.Livinghouse] disclosed method to be prepared.
1HNMRδ：7.02(d，4H)，6.49(t，2H)，6.14(t，4H)，6.36(t，4H)，0.52(s，12H)，5.01～5.02(m，4H)，5.91(m，2H)，3.37(d，4H)；I.R.：3103w，3078w，2943w，2894w，1637w，1488w，1428w，1372m，1246s，1200s，1075m，1054m，1036w，918m，866m，844s，779s，679s，517m，469m，416s；M.S.：761(100，M
-CH
3)；E.A.：C
30H
36Cl
4Si
2Zr
2 MW：777.04；Cal：C：46.37；H：4.67；Found：C：46.25；H：4.61。
Embodiment 13
Synthetic [HC=CHCH
2CH
2CpZrCl
2]
2[μ, μ-(Me
2Si)
2(C
5H
3)
2]
With two silicon bridge compounds [μ, μ-(Me
2Si)
2(C
5H
4)
2] 2.29g (8.94mmol) and 18.0mmol n-BuLi (1.83M) are under argon shield, normal-temperature reaction 2h obtains ligand L.70 ℃ of addings
CpZrCl
3DME7.28g (17.7mmol) reacts 6.0h, CH
2Cl
2/ n-Hexane recrystallization is separated out white solid, yield 31.5%.
1HNMRδ：7.03(d，4H)，6.13(t，4H，)，6.28(t，4H)，6.48(t，2H)，0.51(s，12H)，4.95～5.01(m，4H)，5.74～5.81(m，2H)，2.70(t，4H)，2.29(d，4H)；IR：3094w，3070w，2927w，2903w，2853w，1637w，1452w，1433w，1372w，1247w，1206m，1194m，1052s，1016w，961w，910m，892w，865w，837s，812s，774s，679w，659w，515m，468m，412m；MS：789(100，M
-CH
3)；EA：C
32H
40Cl
4O
2Si
2Zr
2MW：805.09Cal?C47.73，H5.01；FoundC47.11，H5.11。
Embodiment 14
Synthetic [PhCH
2CpZrCl
2]
2[μ, μ-(Me
2Si)
2(C
5H
3)
2]
With two silicon bridge compounds [μ, μ-(Me
2Si)
2(C
5H
4)
2] 338mg (1.47mmol) and 1.68ml n-BuLi (1.83M) are under argon shield, normal-temperature reaction is spent the night and is obtained ligand L, and 100 ℃ add 1.30g BezylCpZrCl
3DME (2.95mmol) reacts 1.0h.CH
2Cl
2/ n-Hexane recrystallization obtains light yellow crystal.Yield is 56%.
BezylCpZrCl
3DME adopts document [Organometallics 9 (1990) 2426 for E.C.Lund, T.Livinghouse] disclosed method to be prepared.
1HNMRδ：6.14(t，4H)，6.32(t，2H)，6.23(t，4H)，7.01(t，4H)，0.52(s，12H)，3.94(s，4H)，7.14～7.27(m，10H)；I.R.：3443m，3420m，3385m，3107.8w，3077w，3023w，2959.7w，2933.6w，1636.6w，1600.4w，1488.4w，1452w，1404w，1370w，1245m，1197.8m，1076.8m，1052m，1034.8m，959w，939w，867w，840s，814s，780s，704s，679m，513.6m，467.8w，413s；MS：861(100，M
-CH
3)；EA：C
38H
40Cl
4Si
2Zr
2 MW：877.16Cal?C：52.03H：4.60；Found C：51.66H：4.60
Embodiment 15
Synthetic [MeOCH
2CH
2CpZrCl
2]
2[μ, μ-(Me
2Si)
2(C
5H
3)
2]
With two silicon bridge compounds [μ, μ-(Me
2Si)
2(C
5H
4)
2] (1.83mol/L, n-BuLi 5.1mmol) are under argon shield, and normal-temperature reaction obtained ligand L in 3.0 hours, and 60 ℃ add MeOCH with 2.80ml for 604mg (2.48mmol)
2CH
2CpZrDME 2.03g (4.95mmol) reacts 15.0h, CH
2Cl
2/ n-Hexane recrystallization is separated out white solid, yield 66.5%.
MeOCH
2CH
2CpZrCl
3DME adopts document [Organometallics9 (1990) 2426 for E.C.Lund, T.Livinghouse] disclosed method to be prepared.
1HNMRδ：7.01(d，4H)，6.27(t，4H)，6.47(t，2H)，6.16(t，4H)，0.49(s，12H)，3.29(s，6H)，2.85(t，4H)，3.51(t，4H)；IR：3090w，3079w，2930w，2872w，2826.6w，1656.2w，1494w，1448w，1394w，1373w，1246m，1200m，1112s，1053m，964m，841s，818s，782s，678m，516m，469m，417m；MS：490(100，M
-MeOCH
2CH
2CpZrCl
2)；EA：C
30H
40Cl
4O
2Si
2Zr
2 MW；813.07 Cal C：44.32 H：4.97；Found?C：44.14H：5.49
Embodiment 16
The 50ml quartz glass tube that contains magnetic stir bar is put into autoclave, high temperature is taken out roasting and is replaced ethylene gas 3 times, 75 ℃ of constant temperature 3 hours adds toluene successively, the complex compound that contains 2.0 μ mol embodiment 1, promotor MAO1.25ml (1.60M) [Al/Ti=500], close the charging opening of autoclave, regulate ethylene pressure to 1.0Mpa, keep pressure, stirring reaction 30min, close the ethene gas cylinder, ethylene gas in the slow emptying autoclave, with 10% acidic alcohol termination reaction, polymkeric substance is transferred in the beaker, standing over night, filter, washing with alcohol is to neutral, and 80 ℃ of constant temperature vacuum-dryings are spent the night, obtain polymkeric substance, activity is 3.76 * 10
5It is 9.80 * 10 that gPE/molTih, viscosimetry measure its molecular weight
4G/mol.
Embodiment 17
The 50ml there-necked flask that contains magnetic stir bar, take out roasting and displacement ethylene gas 3 times, 60 ℃ of constant temperature 3 hours, add toluene successively, contain the complex compound of 2.0 μ mol embodiment 1, promotor MAO2.50ml (1.60M) [Al/Ti=1000], ethylene pressure 1.0 normal atmosphere, stirring reaction 30min closes the ethene gas cylinder, acidic alcohol termination reaction with 10%, polymkeric substance is transferred in the beaker, and standing over night is filtered, washing with alcohol is to neutral, 80 ℃ of constant temperature vacuum-dryings are spent the night, and obtain polymkeric substance, and activity is 2.03 * 10
5It is 1.18 * 10 that gPE/molTih, viscosimetry measure its molecular weight
5G/mol.
Embodiment 18
The 50m quartz glass tube that contains magnetic stir bar is put into autoclave, high temperature is taken out roasting and is replaced ethylene gas 3 times, 75 ℃ of constant temperature 3 hours, add toluene successively, 1-hexene2.0ml, the complex compound that contains 2.0 μ mol embodiment 2, promotor MAO 2.50ml (1.60M) [Al/Ti=1000], ethylene pressure 1.0MPa keeps pressure, stirring reaction 30min, close the ethene gas cylinder, with 10% acidic alcohol termination reaction, polymkeric substance is transferred in the beaker, standing over night, filter, washing with alcohol is to neutral, and 80 ℃ of constant temperature vacuum-dryings are spent the night, obtain polymkeric substance, the copolymerization activity is 5.33 * 10
5It is 1.88g * 10 that gPolymer/molTih, viscosimetry measure its molecular weight
4G/mol, hexene content are 2.31%.
Embodiment 19
The 50ml quartz glass tube that contains magnetic stir bar is put into autoclave, high temperature is taken out roasting and is replaced ethylene gas 3 times, 75 ℃ of constant temperature 3 hours, add toluene successively, 1-hexene2.0ml, the complex compound that contains 2.0 μ mol embodiment 3, promotor MAO 2.50ml (1.60M) [Al/Ti=1000], ethylene pressure 1.0MPa keeps pressure, stirring reaction 30min, close the ethene gas cylinder, with 10% acidic alcohol termination reaction, polymkeric substance is transferred in the beaker, standing over night, filter, washing with alcohol is to neutral, and 80 ℃ of constant temperature vacuum-dryings are spent the night, obtain polymkeric substance, the copolymerization activity is 2.46 * 10
5It is 8.12g * 10 that gPolymer/molTih, viscosimetry measure its molecular weight
4G/mol, hexene content are 3.10%.
Embodiment 20
The 50ml quartz glass tube that contains magnetic stir bar is put into autoclave, high temperature is taken out roasting and is replaced ethylene gas 3 times, 30 ℃ of constant temperature 3 hours, add toluene successively, contain the complex compound of 2.0 μ mol embodiment 4, promotor MAO5.00ml (1.60M) [Al/Ti=2000], ethylene pressure 1.0MPa, stirring reaction 30min closes the ethene gas cylinder, acidic alcohol termination reaction with 10%, polymkeric substance is transferred in the beaker, and standing over night is filtered, washing with alcohol is to neutral, 80 ℃ of constant temperature vacuum-dryings are spent the night, and obtain polymkeric substance, and activity is 4.68 * 10
5It is 4.89 * 10 that gPE/molTih, viscosimetry measure its molecular weight
5G/mol.
Embodiment 21
The 50ml quartz glass tube that contains magnetic stir bar is put into autoclave, high temperature is taken out roasting and is replaced ethylene gas 3 times, 60 ℃ of constant temperature 3 hours, add toluene successively, contain the complex compound of 2.0 μ mol embodiment 5, promotor MAO2.50ml (1.60M) [Al/Ti=1000], ethylene pressure 1.0MPa, stirring reaction 30min closes the ethene gas cylinder, acidic alcohol termination reaction with 10%, polymkeric substance is transferred in the beaker, and standing over night is filtered, washing with alcohol is to neutral, 80 ℃ of constant temperature vacuum-dryings are spent the night, and obtain polymkeric substance, and activity is 2.47 * 10
5It is 6.03 * 10 that gPE/molTih, viscosimetry measure its molecular weight
5G/mol, molecular weight distribution MWD=26.6.
Embodiment 22
The 50ml quartz glass tube that contains magnetic stir bar is put into autoclave, high temperature is taken out roasting and is replaced ethylene gas 3 times, 90 ℃ of constant temperature 3 hours, add toluene successively, contain the complex compound of 2.0 μ mol embodiment 5, promotor MAO2.50ml (1.60M) [Al/Ti=1000], ethylene pressure 1.0MPa, stirring reaction 30min closes the ethene gas cylinder, acidic alcohol termination reaction with 10%, polymkeric substance is transferred in the beaker, and standing over night is filtered, washing with alcohol is to neutral, 80 ℃ of constant temperature vacuum-dryings are spent the night, and obtain polymkeric substance, and activity is 1.10 * 10
5It is 3.03 * 10 that gPE/molTih, viscosimetry measure its molecular weight
5G/mol.
Embodiment 23
The 50ml quartz glass tube that contains magnetic stir bar is put into autoclave, high temperature is taken out roasting and is replaced ethylene gas 3 times, 75 ℃ of constant temperature 3 hours, add toluene successively, contain the complex compound of 2.0 μ mol embodiment 5, promotor MAO0.75ml (1.60M) [Al/Ti=300], ethylene pressure 1.0MPa, stirring reaction 30min closes the ethene gas cylinder, acidic alcohol termination reaction with 10%, polymkeric substance is transferred in the beaker, and standing over night is filtered, washing with alcohol is to neutral, 80 ℃ of constant temperature vacuum-dryings are spent the night, and obtain polymkeric substance, and activity is 2.83 * 10
5It is 5.73 * 10 that gPE/molTih, viscosimetry measure its molecular weight
5G/mol.
Embodiment 24
The 50m quartz glass tube that contains magnetic stir bar is put into autoclave, high temperature is taken out roasting and is replaced ethylene gas 3 times, 75 ℃ of constant temperature 3 hours, add toluene successively, 1-hexene2.0ml, the complex compound that contains 2.0 μ mol embodiment 3, promotor MAO 2.50ml (1.60M) [Al/Ti=1000], ethylene pressure 1.0MPa keeps pressure, stirring reaction 30min, close the ethene gas cylinder, with 10% acidic alcohol termination reaction, polymkeric substance is transferred in the beaker, standing over night, filter, washing with alcohol is to neutral, and 80 ℃ of constant temperature vacuum-dryings are spent the night, obtain polymkeric substance, the copolymerization activity is 4.64 * 10
6It is 1.71g * 10 that gPolymer/molTih, viscosimetry measure its molecular weight
5G/mol, hexene content are 2.65%.
Embodiment 25
The 50ml quartz glass tube that contains magnetic stir bar is put into autoclave, high temperature is taken out roasting and is replaced ethylene gas 3 times, 75 ℃ of constant temperature 3 hours, add toluene successively, 1-hexene2.0ml, the complex compound that contains 2.0 μ mol embodiment 4, promotor MAO 2.50ml (1.60M) [Al/Ti=1000], ethylene pressure 1.0MPa keeps pressure, stirring reaction 30min, close the ethene gas cylinder, with 10% acidic alcohol termination reaction, polymkeric substance is transferred in the beaker, standing over night, filter, washing with alcohol is to neutral, and 80 ℃ of constant temperature vacuum-dryings are spent the night, obtain polymkeric substance, the copolymerization activity is 8.11 * 10
5It is 2.19g * 10 that gPolymer/molTih, viscosimetry measure its molecular weight
4G/mol, hexene content are 2.79%.
Embodiment 26
The 50ml quartz glass tube that contains magnetic stir bar is put into autoclave, high temperature is taken out roasting and is replaced ethylene gas 3 times, 75 ℃ of constant temperature 3 hours, add toluene successively, 1-hexene2.0ml, the complex compound that contains 2.0 μ mol embodiment 5, promotor MAO 2.50ml (1.60M) [Al/Ti=1000], ethylene pressure 1.0MPa keeps pressure, stirring reaction 30min, close the ethene gas cylinder, with 10% acidic alcohol termination reaction, polymkeric substance is transferred in the beaker, standing over night, filter, washing with alcohol is to neutral, and 80 ℃ of constant temperature vacuum-dryings are spent the night, obtain polymkeric substance, the copolymerization activity is 4.53 * 10
5It is 8.41g * 10 that gPolymer/molTih, viscosimetry measure its molecular weight
4G/mol, hexene content are 3.11%.
Embodiment 27
The 50ml quartz glass tube that contains magnetic stir bar is put into autoclave, high temperature is taken out roasting and is replaced ethylene gas 3 times, 90 ℃ of constant temperature 3 hours adds toluene successively, the complex compound that contains 2.0 μ mol embodiment 8, promotor MAO0.37ml (1.60M) [Al/Ti=150], close the charging opening of autoclave, regulate ethylene pressure to 1.0Mpa, keep pressure, stirring reaction 15min, close the ethene gas cylinder, ethylene gas in the slow emptying autoclave, with 10% acidic alcohol termination reaction, polymkeric substance is transferred in the beaker, standing over night, filter, washing with alcohol is to neutral, and 80 ℃ of constant temperature vacuum-dryings are spent the night, obtain polymkeric substance, activity is 8.55 * 10
5It is 5.80 * 10 that gPE/molZrh, viscosimetry measure its molecular weight
5G/mol.
Embodiment 28
The 50ml quartz glass tube that contains magnetic stir bar is put into autoclave, high temperature is taken out roasting and is replaced ethylene gas 3 times, 90 ℃ of constant temperature 3 hours adds toluene successively, the complex compound that contains 2.0 μ mol embodiment 10, promotor MAO0.37ml (1.60M) [Al/Ti=150], close the charging opening of autoclave, regulate ethylene pressure to 1.0Mpa, keep pressure, stirring reaction 15min, close the ethene gas cylinder, ethylene gas in the slow emptying autoclave, with 10% acidic alcohol termination reaction, polymkeric substance is transferred in the beaker, standing over night, filter, washing with alcohol is to neutral, and 80 ℃ of constant temperature vacuum-dryings are spent the night, obtain polymkeric substance, activity is 8.23 * 10
5It is 2.10 * 10 that gPE/molZrh, viscosimetry measure its molecular weight
5G/mol.
Embodiment 29
The 50ml quartz glass tube that contains magnetic stir bar is put into autoclave, high temperature is taken out roasting and is replaced ethylene gas 3 times, 60 ℃ of constant temperature 3 hours adds toluene successively, the complex compound that contains 0.50 μ mol embodiment 9, promotor MAO1.25ml (1.60M) [Al/Ti=500], close the charging opening of autoclave, regulate ethylene pressure to 1.0Mpa, keep pressure, stirring reaction 15min, close the ethene gas cylinder, ethylene gas in the slow emptying autoclave, with 10% acidic alcohol termination reaction, polymkeric substance is transferred in the beaker, standing over night, filter, washing with alcohol is to neutral, and 80 ℃ of constant temperature vacuum-dryings are spent the night, obtain polymkeric substance, activity is 1.14 * 10
7It is 1.30 * 10 that gPE/molZrh, viscosimetry measure its molecular weight
5G/mol.
Embodiment 30
The 50m quartz glass tube that contains magnetic stir bar is put into autoclave, high temperature is taken out roasting and is replaced ethylene gas 3 times, 75 ℃ of constant temperature 3 hours, add toluene successively, 1-hexene2.0ml, the complex compound that contains 2.0 μ mol embodiment 11, promotor MAO 2.50ml (1.60M) [Al/Ti=1000], ethylene pressure 1.0MPa keeps pressure, stirring reaction 15min, close the ethene gas cylinder, with 10% acidic alcohol termination reaction, polymkeric substance is transferred in the beaker, standing over night, filter, washing with alcohol is to neutral, and 80 ℃ of constant temperature vacuum-dryings are spent the night, obtain polymkeric substance, the copolymerization activity is 3.59 * 10
6It is 1.42g * 10 that gPolymer/molZrh, viscosimetry measure its molecular weight
4G/mol, hexene content are 3.65%.
Embodiment 31
The 50ml quartz glass tube that contains magnetic stir bar is put into autoclave, high temperature is taken out roasting and is replaced ethylene gas 3 times, 75 ℃ of constant temperature 3 hours, add toluene successively, 1-hexene2.0ml, the complex compound that contains 2.0 μ mol embodiment 2, promotor MAO 2.50ml (1.60M) [Al/Ti=1000], ethylene pressure 1.0MPa keeps pressure, stirring reaction 15min, close the ethene gas cylinder, with 10% acidic alcohol termination reaction, polymkeric substance is transferred in the beaker, standing over night, filter, washing with alcohol is to neutral, and 80 ℃ of constant temperature vacuum-dryings are spent the night, obtain polymkeric substance, the copolymerization activity is 2.55 * 10
6It is 2.41g * 10 that gPolymer/molZrh, viscosimetry measure its molecular weight
4G/mol, hexene content are 3.15%.
Embodiment 32
The 50ml quartz glass tube that contains magnetic stir bar is put into autoclave, high temperature is taken out roasting and is replaced ethylene gas 3 times, 75 ℃ of constant temperature 3 hours, add toluene successively, contain the complex compound of 2.0 μ mol embodiment 12, promotor MAO0.25ml (1.60M) [Al/Ti=100], ethylene pressure 1.0MPa, stirring reaction 15min closes the ethene gas cylinder, acidic alcohol termination reaction with 10%, polymkeric substance is transferred in the beaker, and standing over night is filtered, washing with alcohol is to neutral, 80 ℃ of constant temperature vacuum-dryings are spent the night, and obtain polymkeric substance, and activity is 5.66 * 10
5It is 5.78 * 10 that gPE/molZrh, viscosimetry measure its molecular weight
5G/mol.
Embodiment 33
The 50ml quartz glass tube that contains magnetic stir bar is put into autoclave, high temperature is taken out roasting and is replaced ethylene gas 3 times, 75 ℃ of constant temperature 3 hours, add toluene successively, contain the complex compound of 2.0 μ mol embodiment 13, promotor MAO5.00ml (1.60M) [Al/Ti=2000], ethylene pressure 1.0MPa, stirring reaction 15min closes the ethene gas cylinder, acidic alcohol termination reaction with 10%, polymkeric substance is transferred in the beaker, and standing over night is filtered, washing with alcohol is to neutral, 80 ℃ of constant temperature vacuum-dryings are spent the night, and obtain polymkeric substance, and activity is 1.g2 * 10
6It is 1.28 * 10 that gPE/molZrh, viscosimetry measure its molecular weight
6G/mol.
Embodiment 34
The 100ml there-necked flask that contains magnetic stir bar, take out roasting and displacement ethylene gas 3 times, 75 ℃ of constant temperature, add toluene successively, contain the complex compound of 2.0 μ mol embodiment 12, promotor MAO 2.5ml (1.60M) [Al/Ti=1000], cumulative volume are 50ml, ethylene pressure 100KPa, stirring reaction 30min, close the ethene gas cylinder, with 10% acidic alcohol termination reaction, polymkeric substance is transferred in the beaker, standing over night, filter, washing with alcohol is to neutral, and 80 ℃ of constant temperature vacuum-dryings are spent the night, obtain polymkeric substance, activity is 3.44 * 10
6It is 2.67 * 10 that gPE/molZrh, viscosimetry measure its molecular weight
5G/mol.
Embodiment 35
The 50ml quartz glass tube that contains magnetic stir bar is put into autoclave, high temperature is taken out roasting and is replaced ethylene gas 3 times, 75 ℃ of constant temperature 3 hours, add toluene successively, contain the complex compound of 2.0 μ mol embodiment 14, promotor MAO0.13ml (1.60M) [Al/Ti=50], ethylene pressure 1.0MPa, stirring reaction 15min closes the ethene gas cylinder, acidic alcohol termination reaction with 10%, polymkeric substance is transferred in the beaker, and standing over night is filtered, washing with alcohol is to neutral, 80 ℃ of constant temperature vacuum-dryings are spent the night, and obtain polymkeric substance, and activity is 4.83 * 10
5It is 4.73 * 10 that gPE/molZrh, viscosimetry measure its molecular weight
5G/mol.
Embodiment 36
The 50ml quartz glass tube that contains magnetic stir bar is put into autoclave, high temperature is taken out roasting and is replaced ethylene gas 3 times, 75 ℃ of constant temperature 3 hours, add toluene successively, contain the complex compound of 2.0 μ mol embodiment 15, promotor MAO2.5ml (1.60M) [Al/Ti=1000], ethylene pressure 1.0MPa, stirring reaction 2.0h closes the ethene gas cylinder, acidic alcohol termination reaction with 10%, polymkeric substance is transferred in the beaker, and standing over night is filtered, washing with alcohol is to neutral, 80 ℃ of constant temperature vacuum-dryings are spent the night, and obtain polymkeric substance, and activity is 7.87 * 10
5It is 6.03 * 10 that gPE/molZrh, viscosimetry measure its molecular weight
5G/mol.
Embodiment 37
The 100ml there-necked flask that contains magnetic stir bar, take out roasting and displacement ethylene gas 3 times, 75 ℃ of constant temperature, add toluene successively, contain the complex compound of 1.0 μ mol embodiment 10, promotor MAO 5.0ml (1.60M) [Al/Ti=2000], cumulative volume are 50ml, ethylene pressure 100KPa, stirring reaction 10min, close the ethene gas cylinder, with 10% acidic alcohol termination reaction, polymkeric substance is transferred in the beaker, standing over night, filter, washing with alcohol is to neutral, and 80 ℃ of constant temperature vacuum-dryings are spent the night, obtain polymkeric substance, activity is 1.34 * 10
7It is 6.42 * 10 that gPE/molZrh, viscosimetry measure its molecular weight
5G/mol.
Claims (9)
1. one kind is limited the configuration Bibridge binucleus cyclopentadienyl metal compound, it is characterized in that structure is as follows:
Wherein:
M represents Ti or Zr;
When M represented Ti, R was alkyl, C3～C10 thiazolinyl or C3～C6 alkoxyl group or the benzyl of C1～C10; When M represented Zr, R was alkyl, C3～C10 thiazolinyl or C3～C6 alkoxyl group, benzyl or the styroyl of C1～C10.
2. restriction configuration Bibridge binucleus cyclopentadienyl metal compound according to claim 1 is characterized in that, R is the alkyl of C1～C4, thiazolinyl or the C3～C5 alkoxyl group of C3～C4.
3. restriction configuration Bibridge binucleus cyclopentadienyl metal compound according to claim 1 is characterized in that R is methyl, propyl group or butyl.
4. restriction configuration Bibridge binucleus cyclopentadienyl metal compound according to claim 1 is characterized in that compound is:
[MeCpTiCl
2]
2[μ，μ-(Me
2Si)
2(C
5H
3)
2]、
[i-PrCpTiCl
2]
2[μ，μ-(Me
2Si)
2(C
5H
3)
2]、
[n-BuCpTiCl
2]
2[μ，μ-(Me
2Si)
2(C
5H
3)
2]、
[HC＝CHCH
2CpTiCl
2]
2[μ，μ-(Me
2Si)
2(C
5H
3)
2]、
[PhCH
2CpTiCl
2]
2[μ，μ-(Me
2Si)
2(C
5H
3)
2]、
[MeCpZrCl
2]
2[μ，μ-(Me
2Si)
2(C
5H
3)
2]、
[n-PrCpZrCl
2]
2[μ，μ-(Me
2Si)
2(C
5H
3)
2]、
[(CH
3)
2CHCpZrCl
2]
2[μ，μ-(Me
2Si)
2(C
5H
3)
2]、
[n-BuCpZrCl
2]
2[μ，μ-(Me
2Si)
2(C
5H
3)
2]、
[Ph(CH
2)
2CpZrCl
2]
2[μ，μ-(Me
2Si)
2(C
5H
3)
2]、
[HC＝CHCH
2CpZrCl
2]
2[μ，μ-(Me
2Si)
2(C
5H
3)
2]、
[HC=CHCH
2CH
2CpZrCl
2]
2[μ, μ-(Me
2Si)
2(C
5H
3)
2] or
[PhCH
2CpZrCl
2]
2[μ，μ-(Me
2Si)
2(C
5H
3)
2]。
5. a restriction configuration Bibridge binucleus cyclopentadienyl metal compound is characterized in that described compound is [MeOCH
2CH
2CpZrCl
2]
2[μ, μ-(Me
2Si)
2(C
5H
3)
2].
6. according to the preparation method of the said restriction configuration of claim 1 Bibridge binucleus cyclopentadienyl metal compound, it is characterized in that, comprise the steps:
With ligand L and RCpMCl
3Place solvent, react under inert atmosphere, temperature of reaction is-78～100 ℃, and the reaction times is 1.0～24 hours, collects target product then from reaction product;
Wherein: said ligand L structure is as follows:
Said RCpMCl
3Structure be in following one:
Wherein:
R is described with claim 1.
7. method according to claim 6 is characterized in that, temperature of reaction is 0-25 ℃, and the reaction times is 2.0-10 hour.
8. method according to claim 6 is characterized in that RCpTiCl
3With the molar ratio of ligand L be: 2.0～2.5: 1.
9. the application of restriction configuration Bibridge binucleus cyclopentadienyl metal compound according to claim 1 is characterized in that, as catalyzer, is used for the copolymerization of alhpa olefin.
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| Title |
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| Isolation and Structural Characterization of cis- andtrans-Forms....... Corey, Joyce Y., Huhmann, Jean L., Rath, Nigam P.Inorganic Chemistry,Vol.34 No.12. 1995 * |
| Isolation and Structural Characterization of cis-andtrans-Forms.......Corey,Joyce Y.,Huhmann,Jean L.,Rath,Nigam P.Inorganic Chemistry,Vol.34 No.12. 1995 * |
| Polymerization and metathesis reactions. XXII....... Lang, Heinrich, et al.Journal of Organometallic Chemistry,Vol.490 No.1-2. 1995 * |
| Polymerization and metathesis reactions. XXII.......Lang,Heinrich,et al.Journal of Organometallic Chemistry,Vol.490 No.1-2. 1995 * |
| Synthesis, structure and polymerization catalytic propertiesof....... Xu, Shansheng, et al.Journal of Organometallic Chemistry,Vol.645 No.1-2. 2002 * |
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