CN101880295A - Constraint geometrical rear-earth complex and preparing method and application thereof in styrene syndiotactic polymerization - Google Patents

Constraint geometrical rear-earth complex and preparing method and application thereof in styrene syndiotactic polymerization Download PDF

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CN101880295A
CN101880295A CN 201010122657 CN201010122657A CN101880295A CN 101880295 A CN101880295 A CN 101880295A CN 201010122657 CN201010122657 CN 201010122657 CN 201010122657 A CN201010122657 A CN 201010122657A CN 101880295 A CN101880295 A CN 101880295A
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CN101880295B (en
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崔冬梅
简忠保
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The invention relates to a constraint geometrical rear-earth complex and a preparing method and an application thereof in styrene syndiotactic polymerization. The constraint geometrical rear-earth complex has a molecular formula [R1-(3-R2-R3-5-R4-6-R5)C5N]LnX2 having a structural formula as follows. The constraint geometrical rear-earth geometrical rear-earth complex and organic boron salt form a catalytic system with a molar ratio of 2:1-1:2, which can catalyze polymerization of the styrene in toluene or chlorobenzol solvent to prepare the syndiotactic styrene. When the polymerization of styrene is catalyzed, within a range of -20 to 80 DEG. C, a monomer conversion rate can be up to 100%, and activity can be up to 1.25*10 to the 7th power gmol Ln-1h-1, and the syndiotactic grade of synthesized polystyrene is up to 100%, a melting point is within a range of 266-272 DEG. C, a number-average molar mass is within a range of 0.046-1 million, and ae minimum molecular weight distribution is 1.30.

Description

Constraint geometrical rear-earth title complex and method for making and the application of this title complex in syndiotactic polymerization of phenylethylene
Technical field
The present invention relates to constraint geometrical rear-earth title complex and method for making and the application of this title complex in syndiotactic polymerization of phenylethylene.
Background technology
The synthetic of polystyrene mainly realized by radical polymerization, anionoid polymerization, cationoid polymerisation and Ziegler-Natta catalyst catalyzed polymerization.According to the difference of steric configuration, polystyrene can be divided into random polystyrene, syndiotactic polystyrene and isotactic polyphenylacetylene.Traditional radical polymerization, anionoid polymerization and cationoid polymerisation mainly obtain random polystyrene, the polymerizing styrene catalyzed isotactic polyphenylacetylene that mainly obtains of Ziegler-Natta catalyst, and high syndiotactic polystyrene was just realized (N.Ishihara by Japanese Idemitsu Kosan company by the metallocene catalyst catalyzed polymerization that uses titanium up to 1986, T.Seimiya, M.Kuramoto and M.Uoi, Macromolecules, 1986,19,2464; EP210615A2 (1987); US5,252,693A1 (1993)).Syndiotactic polystyrene is because its superior character, and for example high-melting-point, high crystalline, high elastic coefficient, low-k, low loss factors and good heat-resisting anti-solvent become a kind of material that haves a great attraction industrial.Since first invention titanium complex of Japanese Idemitsu Kosan company in 1986 can styrene catalyzed high syndiotactic polymerization, investigators have developed a series of titanium catalyst system, and applied for a series of patents, major cause is the titanium complex catalyst system, as Cp*TiCl 3/ MAO and Cp*TiR 3/ B (C 6F 5) 3, to styrene polymerization the time, have very high catalytic activity and have simultaneously very high between normality (N.Ishihara, M.Kuramoto and M.Uoi, Macromolecules, 1988,21,3356; C.Pellecchia, D.Pappalardo, L.Oliva, and A.Zambelli, J.Am.Chem.Soc., 1995,117,6593; Q.Wang, R.Quyoum, D.J.Gillis, M.J.Tudoret, D.Jeremic, B.K.Hunter and M.C.Baird, Organometallics, 1996,15,693; S.Ya.Knjazhanski, G.Cadenas, M.Garcia, C.M.Perez, I.E.Nifant ' ev, I.A.Kashulin, P.V.Ivchenko and K.Lyssenko, Organometallics, 2002,21,3094; A.Zambelli, L.Oliva and C.Pellecchia, Macromolecules, 1989,22,2129; D.Liguori, R.Centore, A.Tuzi, F.Grisi, I.Sessa and A.Zambelli, Macromolecules, 2003,36,5451 etc.).Yet, seldom report is only arranged for the polymerizing styrene catalyzed instrument of rare earth metal complex.Some study group have reported that rare earth metal complex can obtain random polystyrene (Z.Shen, Polym.J., 1990,22,919 to be low to moderate moderate living polymerization vinylbenzene; F.Yuan, Q.Shen and J.Sun, J.Organomet.Chem., 1997,538,241; A.V.Khvostov, V.K.Belsky, A.I.Sizov, B.M.Bulychev and N.B.Ivchenko, J.Organomet.Chem., 1997,531,19; S.Bogaert, J.F.Carpentier, T.Chenal, A.Mortreux and G.Ricart, Macromol.Chem.Phys., 2000,201,1813; K.C.Hultzsch, P.Voth, K.Beckerle and T.P.Spaniol, Organometallics, 2000,19,228).Yasuda study group has reported that the alkylate of single luxuriant lanthanum obtains rich syndiotactic polystyrene (K.Tanaka, M.Furo, E.Ihara and H.Yasuda, J.Polym.Sci.A:Polym.Chem., 2001,39,1382) with lower living polymerization vinylbenzene.Wakatsuki study group in 2000 has reported that samarium complex can be with very high active catalytic polymerizing styrene, but the polystyrene that obtains is random (Z.Hou, Y.Zhang, H.Tezuka, P.Xie, O.Tardif, T.A.Koizumi.H.Yamazaki and Y.Wakatsuki, J.Am.Chem.Soc., 2000,122,10533).Up to 2004, the styrene catalyzed high syndiotactic polymerization of rare earth metal complex was just obtained important breakthrough truly.Carpentier study group has reported rare earth metal allylic cpd [Cp-CMe 2-Flu] Ln (C 3H 5) (THF) the high syndiotactic polymerization of component catalyst vinylbenzene that can place an order at 60 ℃ polymerization temperature, polyreaction has very high activity, normality between the polystyrene that obtains (rrrr) reaches as high as 100%, fusing point is (E.Kirillov, C.W.Lehmann, A.Razavi and J.F.Carpentier in 257～263 ℃ of scopes, J.Am.Chem.Soc., 2004,126,12240; EP1582536 A1; US2006/0116278 A1; US7,241,849B2).Almost simultaneously, Hou study group has reported single cyclopentadienyl rare-earth metal alkylate (C 5Me 4SiMe 3) Ln (CH 2SiMe 3) 2(THF) under the effect of organic boron salt, the high syndiotactic polymerization of energy double-component catalyst vinylbenzene, polymerization activity is up to 1.36 * 10 7Gmol Ln -1h -1, normality between the polystyrene that obtains (rrrr) reaches as high as 100%, and fusing point is (Y.Luo, J.Baldamus and Z.Hou, J.Am.Chem.Soc., 2004,126,13910 in 268～273 ℃ of scopes; US2007/0232758A1).The rare earth metal complex that has luxuriant or assorted cyclopentadienyl ligand more subsequently also is reported in the styrene catalyzed high syndiotactic polymerization of energy (F.Jaroschik under the promotor effect, T.Shima, X.Li, K.Mori, L.Ricard, X.F.Le Goff, F.Nief and Z.Hou, Organometallics, 2007,26,5654; A.S.Rodrigues, E.Kirillov, C.W.Lehmann, T.Roisnel, B.Vuillemin, A.Razavi and J.F.Carpentier, Chem.Eur.J., 2007,13,5548; M.Nishiura, T.Mashiko and Z.Hou, Chem.Commun., 2008,2019; X.Xu, Y.Cheng and J.Sun, Chem.Eur.J., 2009,15,84; F.Bonnet, C.D.C.Violante, P.Roussel, A.Mortreux and M.Visseaux, Chem.Commun., 2009,3380; X.Fang, X.Li, Z.Hou, J.Assoudand R.Zhao, Organometallics, 2009,28,517).Yet the document that has rare earth metal complex styrene catalyzed syndiotactic polymerization of energy under the effect of organic boron salt promotor of constrained geometry configuration part yet there are no report.
Summary of the invention
One of purpose of the present invention provides the constraint geometrical rear-earth title complex.
Described constraint geometrical rear-earth title complex, molecular formula are [R 1-(3-R 2-4-R 3-5-R 4-6-R 5) C 5N] LnX 2, structural formula is a formula 1:
Figure GSA00000052886900021
Formula 1
R in the formula 1 1Be cyclopentadienyl derivative C 5A 4, indenyl derivative C 9A 6Or fluorenyl derivative C 13A 8, A is the substituting group of cyclopentadienyl, the substituting group of indenyl or the substituting group on the fluorenyl, A is selected from hydrogen, aliphatic hydrocarbyl or aromatic hydrocarbyl; Preferred hydrogen or methyl; R 1Preferred tetramethyl-ring pentadienyl or indenyl; R 2Be the substituting group on the skeleton pyridine ring, be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl or phenyl, preferred hydrogen or methyl; R 3Be the substituting group on the skeleton pyridine ring, be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl or phenyl, preferred hydrogen; R 4Be the substituting group on the skeleton pyridine ring, be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl or phenyl, preferred hydrogen; R 5Be the substituting group on the skeleton pyridine ring, be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl, phenyl, 2,6-3,5-dimethylphenyl, 4-aminomethyl phenyl, mesitylene base, 2,6-diisopropyl phenyl, 2,4,6-triisopropyl phenyl or 2, the 6-di-tert-butyl-phenyl, preferred hydrogen, methyl, phenyl, 2,6-3,5-dimethylphenyl or 2,4,6-triisopropyl phenyl; Ln represents rare earth metal, is selected from Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu, preferred Sc, Y, Nd, Gd or Lu; X is selected from CH 2SiMe 3, CH (SiMe 3) 2, 1,3-C 3H 5, 1,3-C 3H 4(Me) or 1,3-C 3H 3(SiMe 3) 2, preferred CH 2SiMe 3Or 1,3-C 3H 5
Preferred constraint geometrical rear-earth title complex is any one in following 1～28 the title complex:
Title complex 1:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=H, Ln=Sc, X=CH 2SiMe 3
Title complex 2:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=H, Ln=Y, X=CH 2SiMe 3
Title complex 3:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=H, Ln=Nd, X=CH 2SiMe 3
Title complex 4:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=H, Ln=Gd, X=CH 2SiMe 3
Title complex 5:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=H, Ln=Lu, X=CH 2SiMe 3
Title complex 6:R 1=C 5Me 4, R 2=Me, R 3=H, R 4=H, R 5=H, Ln=Sc, X=CH 2SiMe 3
Title complex 7:R 1=C 5Me 4, R 2=Me, R 3=H, R 4=H, R 5=H, Ln=Lu, X=CH 2SiMe 3
Title complex 8:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=Me, Ln=Sc, X=CH 2SiMe 3
Title complex 9:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=Me, Ln=Lu, X=CH 2SiMe 3
Title complex 10:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=2,4,6-( iPr) 3C 6H 2, Ln=Sc, X=CH 2SiMe 3
Title complex 11:R 1=C 9H 6, R 2=H, R 3=H, R 4=H, R 5=H, Ln=Sc, X=CH 2SiMe 3
Title complex 12:R 1=C 9H 6, R 2=H, R 3=H, R 4=H, R 5=2,4,6-( iPr) 3C 6H 2, Ln=Sc, X=CH 2SiMe 3
Title complex 13:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=H, Ln=Sc, X=1,3-C 3H 5
Title complex 14:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=H, Ln=Y, X=1,3-C 3H 5
Title complex 15:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=H, Ln=Nd, X=1,3-C 3H 5
Title complex 16:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=H, Ln=Gd, X=1,3-C 3H 5
Title complex 17:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=H, Ln=Lu, X=1,3-C 3H 5
Title complex 18:R 1=C 5Me 4, R 2=Me, R 3=H, R 4=H, R 5=H, Ln=Sc, X=1,3-C 3H 5
Title complex 19:R 1=C 5Me 4, R 2=Me, R 3=H, R 4=H, R 5=H, Ln=Lu, X=1,3-C 3H 5
Title complex 20:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=Me, Ln=Sc, X=1,3-C 3H 5
Title complex 21:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=Me, Ln=Lu, X=1,3-C 3H 5
Title complex 22:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=C 6H 5, Ln=Sc, X=1,3-C 3H 5
Title complex 23:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=2,6-(Me) 2C 6H 3, Ln=Sc, X=1,3-C 3H 5
Title complex 24:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=2,4,6-( iPr) 3C 6H 2, Ln=Sc, X=1,3-C 3H 5
Title complex 25:R 1=C 9H 6, R 2=H, R 3=H, R 4=H, R 5=H, Ln=Sc, X=1,3-C 3H 5
Title complex 26:R 1=C 9H 6, R 2=H, R 3=H, R 4=H, R 5=H, Ln=Lu, X=1,3-C 3H 5
Title complex 27:R 1=C 9H 6, R 2=H, R 3=H, R 4=H, R 5=2,4,6-( iPr) 3C 6H 2, Ln=Sc, X=1,3-C 3H 5
Title complex 28:R 1=C 9H 6, R 2=H, R 3=H, R 4=H, R 5=2,4,6-( iPr) 3C 6H 2, Ln=Lu, X=1,3-C 3H 5
Two of purpose of the present invention provides the method for making of constraint geometrical rear-earth title complex, comprising: the method for making of (1) constraint geometrical rear-earth alkyl complexes; (2) method for making of rare earth allyl complex with constrained geometry configuration; Be described below respectively:
(1) method for making of constraint geometrical rear-earth alkyl complexes:
Synthetic route is as follows:
Figure GSA00000052886900041
Condition and step are as follows: at N 2Under the protection, constrained geometry configuration part R 1H-(3-R 2-4-R 3-5-R 4-6-R 5) C 5N is dissolved in tetrahydrofuran (THF) and places-78～0 ℃, the concentration of 1 times of amount that adds the mol of described constrained geometry configuration part is the normal hexane solution of 1.0～2.0mol/L n-Butyl Lithium, react after 1 hour, the rare earth trichloride of 1 times of amount that adds the mol of described constrained geometry configuration part, react after 4 hours, add the LiCH of 2 times of amounts of the mol of described constrained geometry configuration part 2SiMe 3, room temperature reaction removed and desolvates after 4 hours, used hexane extraction, concentrated hexane, obtained the constraint geometrical rear-earth alkyl complexes; The chemical formula of described rare earth trichloride is to be LnCl 3, the Ln in the Ln cotype 1 wherein.
(2) method for making of rare earth allyl complex with constrained geometry configuration:
Synthetic route is as follows:
Figure GSA00000052886900042
Condition and step are as follows: at N 2Under the protection, constrained geometry configuration part R 1H-(3-R 2-4-R 3-5-R 4-6-R 5) C 5N is dissolved in tetrahydrofuran (THF) and places-78～0 ℃, the concentration of 1 times of amount that adds the mol of described constrained geometry configuration part is the hexane solution of 1.0～2.0mol/L n-Butyl Lithium, react after 1 hour, the rare earth trichloride of 1 times of amount that adds the mol of described constrained geometry configuration part, react after 4 hours, add the C of 2 times of amounts of the mol of described constrained geometry configuration part 3H 5MgCl, room temperature reaction removed and desolvate after 12 hours, with the toluene extraction, concentrated toluene, obtained rare earth allyl complex with constrained geometry configuration; The chemical formula of described rare earth chloride is to be LnCl 3, the Ln in the Ln cotype 1 wherein.
The sign that the constraint geometrical rear-earth alkyl complexes of above-mentioned gained and rare earth allyl complex with constrained geometry configuration all pass through nuclear-magnetism, single crystal diffraction and ultimate analysis.Specifically see embodiment.
Three of purpose of the present invention provides the application of constraint geometrical rear-earth title complex in syndiotactic polymerization of phenylethylene.
Described constraint geometrical rear-earth title complex is used for the catalyst system of syndiotactic polymerization of phenylethylene; This catalyst system was made up of than 2: 1～1: 2 by mol constraint geometrical rear-earth title complex and organic boron salt two components;
Described organic boron salt is: [Ph 3C] [B (C 6F 5) 4], [PhNMe 2H] [BPh 4], [PhNMe 2H] [B (C 6F 5) 4] or B (C 6F 5) 3, preferred [Ph 3C] [B (C 6F 5) 4].
The preparation method's of the described catalyst system that is used for syndiotactic polymerization of phenylethylene step and condition are as follows:
With molecular formula is [R 1-(3-R 2-4-R 3-5-R 4-6-R 5) C 5N] LnX 2The constraint geometrical rear-earth title complex and be organic boron salt of 0.5～2 times of mol amount of selected constraint geometrical rear-earth title complex, by proportioning at C 6～C 7Aromatic hydrocarbon solvent in mix, obtain the catalyst system of homogeneous syndiotactic polymerization of phenylethylene.
The described catalyst system that is used for syndiotactic polymerization of phenylethylene, the step and the condition of method that is used to prepare syndiotactic polystyrene is as follows:
Get the toluene or the chlorobenzene solution that are used for the catalyst system of syndiotactic polymerization of phenylethylene by described, place the reactor of handling through anhydrous, anaerobic, to count ratio be 100: 1～1000: 1 to the mol of constraint geometrical rear-earth title complex in the volume L of described solvent and the described catalyst system; Add styrene monomer, the mol ratio of the constraint geometrical rear-earth title complex in styrene monomer and the described catalyst system is 250: 1～4000: 1, and polyreaction was carried out under-20～80 ℃ 1～30 minute.The adding volumetric concentration is 10% ethanol solution hydrochloride termination polyreaction, pour reaction soln in methyl alcohol sedimentation, get polystyrene white solid powder, again this polystyrene white solid powder is placed vacuum drying oven dry, obtain exsiccant polystyrene white solid powder.
The number-average molecular weight of the syndiotactic polystyrene of above-mentioned gained and molecular weight distribution are measured with high-temperature gel permeation chromatography instrument (GPC), and fusing point is measured with DSC, normality between polystyrene (rrrr) proton nmr spectra ( 1H NMR) and carbon spectrum ( 13C NMR) wave spectrum calculates.Specifically see embodiment.
Beneficial effect: constraint geometrical rear-earth title complex of the present invention has synthetic simple, and yield is up to 41%～64%.The styrene catalyzed syndiotactic polymerization reaction of the catalyst system that itself and organic boron salt are formed has the feature of controllable polymerization.When polymerizing styrene catalyzed, monomer conversion reaches as high as 100%, and activity reaches as high as 1.25 * 10 7G mol Ln -1h -1, normality (rrrr) reaches as high as 100% between institute's synthetic polystyrene, and fusing point is in 266～272 ℃ of scopes, and number-average molecular weight is in 4.6～1,000,000 scopes, and molecular weight distribution is minimum to reach 1.30.
Embodiment
It is as follows that title complex prepares embodiment:
Title complex prepares the preparation of embodiment 1 title complex 1
Figure GSA00000052886900061
Under-78 ℃ of conditions, be that (1.2mL 1.2mmol) is added drop-wise to 1-(2-pyridyl)-2,3,4, and (0.24g is in the solution of tetrahydrofuran (THF) 1.2mmol) (20mL) for 5-tetramethyl-ring pentadiene for the hexane solution of the n-Butyl Lithium of 1.0mol/L with concentration.Reaction solution under this temperature the reaction 1 hour after with ScCl 3(0.18g 1.2mmol) is added in the above-mentioned reaction solution, reacts after 4 hours, with LiCH 2SiMe 3(0.23g 2.4mmol) adds, and room temperature reaction is after 4 hours, and vacuum is taken out and desolvated, and resistates hexane extraction, concentrated hexane solution obtain red crystals title complex 1 0.27g altogether, productive rate 54%.Ultimate analysis target compound molecular formula is C 22H 38NSi 2Sc (%): C, 62.84; H, 9.25; N, 3.28.
Title complex prepares the preparation of embodiment 2 title complex 2-5
Among the preparation method of title complex 2-5, except the change of reactant rare earth trichloride, other condition and step prepare embodiment 1 with title complex, the constraint geometrical rear-earth alkyl complexes 2-5 and result such as the table 1 that obtain:
Table 1 constraint geometrical rear-earth alkyl complexes 2-5
Title complex The rare earth trichloride The target compound molecular formula Ultimate analysis (%) Productive rate (%)
??2 ??YCl 3 ??C 22H 38NSi 2Y ??C，56.87；H，8.36；N，2.97 ??48
??3 ??NdCl 3 ??C 22H 38NSi 2Nd ??C，49.81；H，7.46；N，2.61 ??45
??4 ??GdCl 3 ??C 22H 38NSi 2Gd ??C，49.52；H，7.30；N，2.56 ??63
??5 ??LuCl 3 ??C 22H 38NSi 2Lu ??C，47.86；H，7.05；N，2.48 ??61
Title complex prepares the preparation of embodiment 3 title complexs 6
Under-40 ℃ of conditions, with concentration be the n-Butyl Lithium of 1.5mol/L hexane solution (0.8mL 1.2mmol) is added drop-wise to 1-[2-(3-methyl) pyridyl]-2,3,4, (0.26g is in the solution of tetrahydrofuran (THF) 1.2mmol) (20mL) for 5-tetramethyl-ring pentadiene.Reaction solution under this temperature the reaction 1 hour after with ScCl 3(0.18g 1.2mmol) is added in the above-mentioned reaction solution, reacts after 4 hours, with LiCH 2SiMe 3(0.23g 2.4mmol) adds, and room temperature reaction is after 4 hours, and vacuum is taken out and desolvated, and resistates hexane extraction, concentrated hexane solution obtain light red crystal title complex 6 0.30g altogether, productive rate 58%.Ultimate analysis target compound molecular formula is C 23H 40NSi 2Sc (%): C, 63.54; H, 9.42; N, 3.15.
Title complex prepares the preparation of embodiment 4 title complexs 7
Figure GSA00000052886900071
Under-40 ℃ of conditions, with concentration be the n-Butyl Lithium of 1.5mol/L hexane solution (0.8mL 1.2mmol) is added drop-wise to 1-[2-(3-methyl) pyridyl]-2,3,4, (0.26g is in the solution of tetrahydrofuran (THF) 1.2mmol) (20mL) for 5-tetramethyl-ring pentadiene.Reaction solution under this temperature the reaction 1 hour after with LuCl 3(0.34g 1.2mmol) is added in the above-mentioned reaction solution, reacts after 4 hours, with LiCH 2SiMe 3(0.23g 2.4mmol) adds, and room temperature reaction is after 4 hours, and vacuum is taken out and desolvated, and resistates hexane extraction, concentrated hexane solution obtain light red crystal title complex 7 0.41g altogether, productive rate 61%.Ultimate analysis target compound molecular formula is C 23H 40NSi 2Lu (%): C, 48.93; H, 7.00; N, 2.38.
Title complex prepares the preparation of embodiment 5 title complexs 8
Figure GSA00000052886900072
Under 40 ℃ of conditions, with concentration be the n-Butyl Lithium of 1.5mol/L hexane solution (0.8mL 1.2mmol) is added drop-wise to 1-[2-(6-methyl) pyridyl]-2,3,4, (0.26g is in the solution of tetrahydrofuran (THF) 1.2mmol) (20mL) for 5-tetramethyl-ring pentadiene.Reaction solution under this temperature the reaction 1 hour after with ScCl 3(0.18g 1.2mmol) is added in the above-mentioned reaction solution, reacts after 4 hours, with LiCH 2SiMe 3(0.23g 2.4mmol) adds, and room temperature reaction is after 4 hours, and vacuum is taken out and desolvated, and resistates hexane extraction, concentrated hexane solution obtain light red crystal title complex 8 0.25g altogether, productive rate 48%.Ultimate analysis target compound molecular formula is C 23H 40NSi 2Sc (%): C, 63.48; H, 9.38; N, 3.19.
Title complex prepares the preparation of embodiment 6 title complexs 9
Figure GSA00000052886900081
Under-40 ℃ of conditions, with concentration be the n-Butyl Lithium of 1.5mol/L hexane solution (0.8mL 1.2mmol) is added drop-wise to 1-[2-(6-methyl) pyridyl]-2,3,4, (0.26g is in the solution of tetrahydrofuran (THF) 1.2mmol) (20mL) for 5-tetramethyl-ring pentadiene.Reaction solution under this temperature the reaction 1 hour after with LuCl 3(0.34g 1.2mmol) is added in the above-mentioned reaction solution, reacts after 4 hours, with LiCH 2SiMe 3(0.23g 2.4mmol) adds, and room temperature reaction is after 4 hours, and vacuum is taken out and desolvated, and resistates hexane extraction, concentrated hexane solution obtain light red crystal title complex 9 0.31g altogether, productive rate 46%.Ultimate analysis target compound molecular formula is C 23H 40NSi 2Lu (%): C, 49.00; H, 6.97; N, 2.35.
Title complex prepares the preparation of embodiment 7 title complexs 10
Under-40 ℃ of conditions, be that (0.8mL 1.2mmol) is added drop-wise to 1-{2-[6-(2 for the hexane solution of the n-Butyl Lithium of 1.5mol/L with concentration, 4,6-triisopropyl phenyl)] pyridyl-2,3,4, (0.48g is in the solution of tetrahydrofuran (THF) 1.2mmol) (20mL) for 5-tetramethyl-ring pentadiene.Reaction solution under this temperature the reaction 1 hour after with ScCl 3(0.18g 1.2mmol) is added in the above-mentioned reaction solution, reacts after 4 hours, with LiCH 2SiMe 3(0.23g 2.4mmol) adds, and room temperature reaction is after 4 hours, and vacuum is taken out and desolvated, and resistates hexane extraction, concentrated hexane solution obtain light red crystal title complex 10 0.32g altogether, productive rate 42%.Ultimate analysis target compound molecular formula is C 37H 60NSi 2Sc (%): C, 71.48; H, 9.65; N, 2.18.
Title complex prepares the preparation of embodiment 8 title complexs 11
Under-20 ℃ of conditions, be that (0.6mL, (0.23g is in the solution of tetrahydrofuran (THF) 1.2mmol) (20mL) 1.2mmol) to be added drop-wise to 1-(2-pyridyl) indenes for the hexane solution of the n-Butyl Lithium of 2.0mol/L with concentration.Reaction solution under this temperature the reaction 1 hour after with ScCl 3(0.18g 1.2mmol) is added in the above-mentioned reaction solution, reacts after 4 hours, with LiCH 2SiMe 3(0.23g 2.4mmol) adds, and room temperature reaction is after 4 hours, and vacuum is taken out and desolvated, and resistates hexane extraction, concentrated hexane solution obtain scarlet crystal title complex 11 0.26g altogether, productive rate 53%.Ultimate analysis target compound molecular formula is C 22H 32NSi 2Sc (%): C, 63.98; H, 7.69; N, 3.31.
Title complex prepares 12 preparations of embodiment 9 title complexs
Figure GSA00000052886900091
Under 0 ℃ of condition, with concentration be the n-Butyl Lithium of 2.0mol/L hexane solution (0.6mL 1.2mmol) is added drop-wise to 1-{2-[6-(2,4,6-triisopropyl phenyl)] pyridyl (0.48g is in the solution of tetrahydrofuran (THF) 1.2mmol) (20mL) for indenes.Reaction solution under this temperature the reaction 1 hour after with ScCl 3(0.18g 1.2mmol) is added in the above-mentioned reaction solution, reacts after 4 hours, with LiCH 2SiMe 3(0.23g 2.4mmol) adds, and room temperature reaction is after 4 hours, and vacuum is taken out and desolvated, and resistates hexane extraction, concentrated hexane solution obtain scarlet crystal title complex 12 0.52g altogether, productive rate 42%.Ultimate analysis target compound molecular formula is C 37H 54NSi 2Sc (%): C, 72.18; H, 8.69; N, 2.17.
Title complex prepares the preparation of embodiment 10 title complexs 13
Figure GSA00000052886900092
Under-78 ℃ of conditions, be that (1.2mL 1.2mmol) is added drop-wise to 1-(2-pyridyl)-2,3,4, and (0.24g is in the solution of tetrahydrofuran (THF) 1.2mmol) (20mL) for 5-tetramethyl-ring pentadiene for the hexane solution of the n-Butyl Lithium of 1.0mol/L with concentration.Reaction solution under this temperature the reaction 1 hour after with ScCl 3(0.18g 12mmol) is added in the above-mentioned reaction solution, reacts after 4 hours, with C 3H 5MgCl (1.2mL, 2.4mmol, 2Min THF) adds, and room temperature reaction is after 12 hours, and vacuum is taken out and desolvated, and resistates extracts with toluene, and concentrated toluene solution obtains reddish yellow crystal title complex 13 0.25g altogether, productive rate 64%.Ultimate analysis target compound molecular formula is C 20H 26NSc (%): C, 73.52; H, 7.90; N, 4.18.
Title complex prepares the preparation of embodiment 11 title complexs 14
Figure GSA00000052886900101
Under-78 ℃ of conditions, be that (1.2mL 1.2mmol) is added drop-wise to 1-(2-pyridyl)-2,3,4, and (0.24g is in the solution of tetrahydrofuran (THF) 1.2mmol) (20mL) for 5-tetramethyl-ring pentadiene for the hexane solution of the n-Butyl Lithium of 1.0mol/L with concentration.Reaction solution under this temperature the reaction 1 hour after with YCl 3(0.23g 1.2mmol) is added in the above-mentioned reaction solution, reacts after 4 hours, with C 3H 5MgCl (12mL, 2.4mmol, 2Min THF) adds, and room temperature reaction is after 12 hours, and vacuum is taken out and desolvated, and resistates extracts with toluene, and concentrated toluene solution obtains reddish yellow crystal title complex 14 0.26g altogether, productive rate 58%.Ultimate analysis target compound molecular formula is C 20H 26NY (%): C, 64.80; H, 7.01; N, 3.68.
Title complex prepares the preparation of embodiment 12 title complexs 15
Under-40 ℃ of conditions, be that (1.2mL 1.2mmol) is added drop-wise to 1-(2-pyridyl)-2,3,4, and (0.24g is in the solution of tetrahydrofuran (THF) 1.2mmol) (20mL) for 5-tetramethyl-ring pentadiene for the hexane solution of the n-Butyl Lithium of 1.0mol/L with concentration.Reaction solution under this temperature the reaction 1 hour after with NdCl 3(0.30g 1.2mmol) is added in the above-mentioned reaction solution, reacts after 4 hours, with C 3H 5MgCl (1.2mL, 2.4mmol, 2Min THF) adds, and room temperature reaction is after 12 hours, and vacuum is taken out and desolvated, and resistates extracts with toluene, and concentrated toluene solution obtains reddish yellow crystal title complex 15 0.28g altogether, productive rate 55%.Ultimate analysis target compound molecular formula is C 20H 26NNd (%): C, 56.37; H, 6.06; N, 3.21.
Title complex prepares the preparation of embodiment 13 title complexs 16
Under-20 ℃ of conditions, be that (1.2mL 1.2mmol) is added drop-wise to 1-(2-pyridyl)-2,3,4, and (0.24g is in the solution of tetrahydrofuran (THF) 1.2mmol) (20mL) for 5-tetramethyl-ring pentadiene for the hexane solution of the n-Butyl Lithium of 1.0mol/L with concentration.Reaction solution under this temperature the reaction 1 hour after with GdCl 3(0.32g 1.2mmol) is added in the above-mentioned reaction solution, reacts after 4 hours, with C 3H 5MgCl (1.2mL, 2.4mmol, 2Min THF) adds, and room temperature reaction is after 12 hours, and vacuum is taken out and desolvated, and resistates extracts with toluene, and concentrated toluene solution obtains reddish yellow crystal title complex 16 0.32g altogether, productive rate 61%.Ultimate analysis target compound molecular formula is C 20H 26NGd (%): C, 54.58; H, 5.89; N, 3.11.
Title complex prepares the preparation of embodiment 14 title complexs 17
Figure GSA00000052886900111
Under 0 ℃ of condition, be that (1.2mL 1.2mmol) is added drop-wise to 1-(2-pyridyl)-2,3,4, and (0.24g is in the solution of tetrahydrofuran (THF) 1.2mmol) (20mL) for 5-tetramethyl-ring pentadiene for the hexane solution of the n-Butyl Lithium of 1.0mol/L with concentration.Reaction solution under this temperature the reaction 1 hour after with LuCl 3(0.34g 1.2mmol) is added in the above-mentioned reaction solution, reacts after 4 hours, with C 3H 5MgCl (1.2mL, 2.4mmol, 2Min THF) adds, and room temperature reaction is after 12 hours, and vacuum is taken out and desolvated, and resistates extracts with toluene, and concentrated toluene solution obtains reddish yellow crystal title complex 17 0.34g altogether, productive rate 63%.Ultimate analysis target compound molecular formula is C 20H 26NLu (%): C, 52.42; H, 5.61; N, 2.99.
Title complex prepares the preparation of embodiment 15 title complexs 18
Figure GSA00000052886900112
Under-40 ℃ of conditions, with concentration be the n-Butyl Lithium of 1.5mol/L hexane solution (0.8mL 1.2mmol) is added drop-wise to 1-[2-(3-methyl) pyridyl]-2,3,4, (0.26g is in the solution of tetrahydrofuran (THF) 1.2mmol) (20mL) for 5-tetramethyl-ring pentadiene.Reaction solution under this temperature the reaction 1 hour after with ScCl 3(0.18g 1.2mmol) is added in the above-mentioned reaction solution, reacts after 4 hours, with C 3H 5MgCl (1.2mL, 2.4mmol, 2Min THF) adds, and room temperature reaction is after 12 hours, and vacuum is taken out and desolvated, and resistates extracts with toluene, and concentrated toluene solution obtains reddish yellow crystal title complex 18 0.22g altogether, productive rate 53%.Ultimate analysis target compound molecular formula is C 21H 28NSc (%): C, 74.11; H, 8.21; N, 4.02.
Title complex prepares the preparation of embodiment 16 title complexs 19
Figure GSA00000052886900121
Under-40 ℃ of conditions, with concentration be the n-Butyl Lithium of 1.5mol/L hexane solution (0.8mL 1.2mmol) is added drop-wise to 1-[2-(3-methyl) pyridyl]-2,3,4, (0.26g is in the solution of tetrahydrofuran (THF) 1.2mmol) (20mL) for 5-tetramethyl-ring pentadiene.Reaction solution under this temperature the reaction 1 hour after with LuCl 3(0.34g 1.2mmol) is added in the above-mentioned reaction solution, reacts after 4 hours, with C 3H 5MgCl (1.2mL, 2.4mmol, 2Min THF) adds, and room temperature reaction is after 12 hours, and vacuum is taken out and desolvated, and resistates extracts with toluene, and concentrated toluene solution obtains reddish yellow crystal title complex 19 0.29g altogether, productive rate 51%.Ultimate analysis target compound molecular formula is C 21H 28NLu (%): C, 53.53; H, 5.89; N, 2.88.
Title complex prepares the preparation of embodiment 17 title complexs 20
Figure GSA00000052886900122
Under-40 ℃ of conditions, with concentration be the n-Butyl Lithium of 1.5mol/L hexane solution (0.8mL 1.2mmol) is added drop-wise to 1-[2-(6-methyl) pyridyl]-2,3,4, (0.26g is in the solution of tetrahydrofuran (THF) 1.2mmol) (20mL) for 5-tetramethyl-ring pentadiene.Reaction solution under this temperature the reaction 1 hour after with ScCl 3(0.18g 1.2mmol) is added in the above-mentioned reaction solution, reacts after 4 hours, with C 3H 5MgCl (1.2mL, 2.4mmol, 2Min THF) adds, and room temperature reaction is after 12 hours, and vacuum is taken out and desolvated, and resistates extracts with toluene, and concentrated toluene solution obtains reddish yellow crystal title complex 20 0.20g altogether, productive rate 48%.Ultimate analysis target compound molecular formula is C 21H 28NSc (%): C, 74.01; H, 8.25; N, 3.98.
Title complex prepares the preparation of embodiment 18 title complexs 21
Figure GSA00000052886900123
Under-40 ℃ of conditions, with concentration be the n-Butyl Lithium of 1.5mol/L hexane solution (0.8mL 1.2mmol) is added drop-wise to 1-[2-(6-methyl) pyridyl]-2,3,4, (0.26g is in the solution of tetrahydrofuran (THF) 1.2mmol) (20mL) for 5-tetramethyl-ring pentadiene.Reaction solution under this temperature the reaction 1 hour after with LuCl 3(0.34g 1.2mmol) is added in the above-mentioned reaction solution, reacts after 4 hours, with C 3H 5MgCl (1.2mL, 2.4mmol, 2Min THF) adds, and room temperature reaction is after 12 hours, and vacuum is taken out and desolvated, and resistates extracts with toluene, and concentrated toluene solution obtains reddish yellow crystal title complex 21 0.23g altogether, productive rate 41%.Ultimate analysis target compound molecular formula is C 21H 28NLu (%): C, 53.45; H, 5.94; N, 2.85.
Title complex prepares the preparation of embodiment 19 title complexs 22
Figure GSA00000052886900131
Under-40 ℃ of conditions, with concentration be the n-Butyl Lithium of 15mol/L hexane solution (0.8mL 1.2mmol) is added drop-wise to 1-[2-(6-phenyl) pyridyl]-2,3,4, (0.33g is in the solution of tetrahydrofuran (THF) 1.2mmol) (20mL) for 5-tetramethyl-ring pentadiene.Reaction solution under this temperature the reaction 1 hour after with ScCl 3(0.18g 1.2mmol) is added in the above-mentioned reaction solution, reacts after 4 hours, with C 3H 5MgCl (1.2mL, 2.4mmol, 2Min THF) adds, and room temperature reaction is after 12 hours, and vacuum is taken out and desolvated, and resistates extracts with toluene, and concentrated toluene solution obtains reddish yellow crystal title complex 22 0.21g altogether, productive rate 44%.Ultimate analysis target compound molecular formula is C 26H 30NSc (%): C, 77.48; H, 7.40; N, 3.38.
Title complex prepares the preparation of embodiment 20 title complexs 23
Figure GSA00000052886900132
Under-40 ℃ of conditions, be that (0.8mL 1.2mmol) is added drop-wise to 1-{2-[6-(2 for the hexane solution of the n-Butyl Lithium of 1.5mol/L with concentration, the 6-3,5-dimethylphenyl)] pyridyl }-2,3,4, (0.36g is in the solution of tetrahydrofuran (THF) 1.2mmol) (20mL) for 5-tetramethyl-ring pentadiene.Reaction solution under this temperature the reaction 1 hour after with ScCl 3(0.18g 1.2mmol) is added in the above-mentioned reaction solution, reacts after 4 hours, with C 3H 5MgCl (1.2mL, 2.4mmol, 2Min THF) adds, and room temperature reaction is after 12 hours, and vacuum is taken out and desolvated, and resistates extracts with toluene, and concentrated toluene solution obtains reddish yellow crystal title complex 23 0.25g altogether, productive rate 48%.Ultimate analysis target compound molecular formula is C 28H 34NSc (%): C, 78.00; H, 7.88; N, 3.16.
Title complex prepares the preparation of embodiment 21 title complexs 24
Figure GSA00000052886900141
Under-40 ℃ of conditions, be that (0.8mL 1.2mmol) is added drop-wise to 1-{2-[6-(2 for the hexane solution of the n-Butyl Lithium of 1.5mol/L with concentration, 4,6-triisopropyl phenyl)] pyridyl-2,3,4, (0.48g is in the solution of tetrahydrofuran (THF) 1.2mmol) (20mL) for 5-tetramethyl-ring pentadiene.Reaction solution under this temperature the reaction 1 hour after with ScCl 3(0.18g 1.2mmol) is added in the above-mentioned reaction solution, reacts after 4 hours, with C 3H 5MgCl (1.2mL, 2.4mmol, 2Min THF) adds, and room temperature reaction is after 12 hours, and vacuum is taken out and desolvated, and resistates extracts with toluene, and concentrated toluene solution obtains reddish yellow crystal title complex 24 0.30g altogether, productive rate 48%.Ultimate analysis target compound molecular formula is C 35H 48NSc (%): C, 79.48; H, 7.03; N, 2.54.
Title complex prepares the preparation of embodiment 22 title complexs 25
Figure GSA00000052886900142
Under 0 ℃ of condition, be that (0.6mL, (0.23g is in the solution of tetrahydrofuran (THF) 1.2mmol) (20mL) 1.2mmol) to be added drop-wise to 1-(2-pyridyl) indenes for the hexane solution of the n-Butyl Lithium of 2.0mol/L with concentration.Reaction solution under this temperature the reaction 1 hour after with ScCl 3(0.18g 1.2mmol) is added in the above-mentioned reaction solution, reacts after 4 hours, with C 3H 5MgCl (1.2mL, 2.4mmol, 2Min THF) adds, and room temperature reaction is after 12 hours, and vacuum is taken out and desolvated, and resistates extracts with toluene, and concentrated toluene solution obtains yellow crystals title complex 25 0.16g altogether, productive rate 43%.Ultimate analysis target compound molecular formula is C 20H 20NSc (%): C, 75.00; H, 6.21; N, 4.32.
Title complex prepares the preparation of embodiment 23 title complexs 26
Under 0 ℃ of condition, be that (0.6mL, (0.23g is in the solution of tetrahydrofuran (THF) 1.2mmol) (20mL) 1.2mmol) to be added drop-wise to 1-(2-pyridyl) indenes for the hexane solution of the n-Butyl Lithium of 2.0mol/L with concentration.Reaction solution under this temperature the reaction 1 hour after with LuCl 3(0.34g 1.2mmol) is added in the above-mentioned reaction solution, reacts after 4 hours, with C 3H 5MgCl (1.2mL, 2.4mmol, 2Min THF) adds, and room temperature reaction is after 12 hours, and vacuum is taken out and desolvated, and resistates extracts with toluene, and concentrated toluene solution obtains yellow crystals title complex 26 0.30g altogether, productive rate 56%.Ultimate analysis target compound molecular formula is C 20H 20NLu (%): C, 53.34; H, 4.39; N, 3.04.
Title complex prepares the preparation of embodiment 24 title complexs 27
Under 0 ℃ of condition, with concentration be the n-Butyl Lithium of 2.0mol/L hexane solution (0.6mL 1.2mmol) is added drop-wise to 1-{2-[6-(2,4,6-triisopropyl phenyl)] pyridyl (0.48g is in the solution of tetrahydrofuran (THF) 1.2mmol) (20mL) for indenes.Reaction solution under this temperature the reaction 1 hour after with ScCl 3(0.18g 1.2mmol) is added in the above-mentioned reaction solution, reacts after 4 hours, with C 3H 5MgCl (1.2mL, 2.4mmol, 2Min THF) adds, and room temperature reaction is after 12 hours, and vacuum is taken out and desolvated, and resistates extracts with toluene, and concentrated toluene solution obtains yellow crystals title complex 27 0.29g altogether, productive rate 56%.Ultimate analysis target compound molecular formula is C 35H 42NSc (%): C, 80.38; H, 8.01; N, 2.58.
Title complex prepares the preparation of embodiment 25 title complexs 28
Figure GSA00000052886900161
Under 0 ℃ of condition, with concentration be the n-Butyl Lithium of 2.0mol/L hexane solution (0.6mL 1.2mmol) is added drop-wise to 1-{2-[6-(2,4,6-triisopropyl phenyl)] pyridyl (0.48g is in the solution of tetrahydrofuran (THF) 1.2mmol) (20mL) for indenes.Reaction solution under this temperature the reaction 1 hour after with LuCl 3(0.34g 1.2mmol) is added in the above-mentioned reaction solution, reacts after 4 hours, with C 3H 5MgCl (1.2mL, 2.4mmol, 2Min THF) adds, and room temperature reaction is after 12 hours, and vacuum is taken out and desolvated, and resistates extracts with toluene, and concentrated toluene solution obtains yellow crystals title complex 28 0.39g altogether, productive rate 50%.Ultimate analysis target compound molecular formula is C 35H 42NLu (%): C, 64.45; H, 6.38; N, 2.07.
The preparation embodiment of catalyst system is as follows:
Catalyst system prepares the preparation of embodiment 1 catalyst system 1
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 1,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 1ml, reacted 2 minutes, catalyst system 1.
Catalyst system prepares the preparation of embodiment 2 catalyst system 2
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 1,5 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 5ml, reacted 2 minutes, catalyst system 2.
Catalyst system prepares the preparation of embodiment 3 catalyst system 3
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 1,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 5ml, reacted 2 minutes, catalyst system 3.
Catalyst system prepares the preparation of embodiment 4 catalyst system 4
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 1,20 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 5ml, reacted 2 minutes, catalyst system 4.
Catalyst system prepares the preparation of embodiment 5 catalyst system 5
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 1,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 10ml, reacted 2 minutes, catalyst system 5.
Catalyst system prepares the preparation of embodiment 6 catalyst system 6
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 1,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the chlorobenzene solvent of 10ml, reacted 2 minutes, catalyst system 6.
Catalyst system prepares the preparation of embodiment 7 catalyst system 7
Under-20 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 1,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 2ml, reacted 2 minutes, catalyst system 7.
Catalyst system prepares the preparation of embodiment 8 catalyst system 8
Under 40 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 1,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 2ml, reacted 2 minutes, catalyst system 8.
Catalyst system prepares the preparation of embodiment 9 catalyst system 9
Under 80 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 1,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 5ml, reacted 2 minutes, catalyst system 9.
Catalyst system prepares the preparation of embodiment 10 catalyst system 10
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 2,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 3ml, reacted 2 minutes, catalyst system 10.
Catalyst system prepares the preparation of embodiment 11 catalyst system 11
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 3,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 5ml, reacted 2 minutes, catalyst system 11.
Catalyst system prepares the preparation of embodiment 12 catalyst system 12
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 4,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 8ml, reacted 2 minutes, catalyst system 12.
Catalyst system prepares the preparation of embodiment 13 catalyst system 13
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 5,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 1ml, reacted 2 minutes, catalyst system 13.
Catalyst system prepares the preparation of embodiment 14 catalyst system 14
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 5,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 5ml, reacted 2 minutes, catalyst system 14.
Catalyst system prepares the preparation of embodiment 15 catalyst system 15
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 5,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 10ml, reacted 2 minutes, catalyst system 15.
Catalyst system prepares the preparation of embodiment 16 catalyst system 16
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 5,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the chlorobenzene solvent of 10ml, reacted 2 minutes, catalyst system 16.
Catalyst system prepares the preparation of embodiment 17 catalyst system 17
Under-20 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 6,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 10ml, reacted 2 minutes, catalyst system 17.
Catalyst system prepares the preparation of embodiment 18 catalyst system 18
Under 80 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 7,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 10ml, reacted 2 minutes, catalyst system 18.
Catalyst system prepares the preparation of embodiment 19 catalyst system 19
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 8,5 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 10ml, reacted 2 minutes, catalyst system 19.
Catalyst system prepares the preparation of embodiment 20 catalyst system 20
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 9,20 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 10ml, reacted 2 minutes, catalyst system 20.
Catalyst system prepares the preparation of embodiment 21 catalyst system 21
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 10,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the chlorobenzene solvent of 10ml, reacted 2 minutes, catalyst system 21.
Catalyst system prepares the preparation of embodiment 22 catalyst system 22
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 11,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 10ml, reacted 2 minutes, catalyst system 22.
Catalyst system prepares the preparation of embodiment 23 catalyst system 23
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 12,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 10ml, reacted 2 minutes, catalyst system 23.
Catalyst system prepares the preparation of embodiment 24 catalyst system 24
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 13,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 1ml, reacted 2 minutes, catalyst system 24.
Catalyst system prepares the preparation of embodiment 25 catalyst system 25
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 13,5 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 5ml, reacted 2 minutes, catalyst system 25.
Catalyst system prepares the preparation of embodiment 26 catalyst system 26
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 13,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 5ml, reacted 2 minutes, catalyst system 26.
Catalyst system prepares the preparation of embodiment 27 catalyst system 27
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 13,20 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 5ml, reacted 2 minutes, catalyst system 27.
Catalyst system prepares the preparation of embodiment 28 catalyst system 28
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 13,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 10ml, reacted 2 minutes, catalyst system 28.
Catalyst system prepares the preparation of embodiment 29 catalyst system 29
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 13,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the chlorobenzene solvent of 10ml, reacted 2 minutes, catalyst system 29.
Catalyst system prepares the preparation of embodiment 30 catalyst system 30
Under-20 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 13,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 2ml, reacted 2 minutes, catalyst system 30.
Catalyst system prepares the preparation of embodiment 31 catalyst system 31
Under 40 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 13,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 2ml, reacted 2 minutes, catalyst system 31.
Catalyst system prepares the preparation of embodiment 32 catalyst system 32
Under 80 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 13,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 5ml, reacted 2 minutes, catalyst system 32.
Catalyst system prepares the preparation of embodiment 33 catalyst system 33
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 14,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 3ml, reacted 2 minutes, catalyst system 33.
Catalyst system prepares the preparation of embodiment 34 catalyst system 34
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 15,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 5ml, reacted 2 minutes, catalyst system 34.
Catalyst system prepares the preparation of embodiment 35 catalyst system 35
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 16,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 8ml, reacted 2 minutes, catalyst system 35.
Catalyst system prepares the preparation of embodiment 36 catalyst system 36
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 17,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 1ml, reacted 2 minutes, catalyst system 36.
Catalyst system prepares the preparation of embodiment 37 catalyst system 37
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 17,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 2ml, reacted 2 minutes, catalyst system 37.
Catalyst system prepares the preparation of embodiment 38 catalyst system 38
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 17,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 4ml, reacted 2 minutes, catalyst system 38.
Catalyst system prepares the preparation of embodiment 39 catalyst system 39
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 17,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 8ml, reacted 2 minutes, catalyst system 39.
Catalyst system prepares the preparation of embodiment 40 catalyst system 40
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 17,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 10ml, reacted 2 minutes, catalyst system 40.
Catalyst system prepares the preparation of embodiment 41 catalyst system 41
Under-20 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 18,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 10ml, reacted 2 minutes, catalyst system 41.
Catalyst system prepares the preparation of embodiment 42 catalyst system 42
Under 80 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 19,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 10ml, reacted 2 minutes, catalyst system 42.
Catalyst system prepares the preparation of embodiment 43 catalyst system 43
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 20,5 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 5ml, reacted 2 minutes, catalyst system 43.
Catalyst system prepares the preparation of embodiment 44 catalyst system 44
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 21,20 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 5ml, reacted 2 minutes, catalyst system 44.
Catalyst system prepares the preparation of embodiment 45 catalyst system 45
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 22,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the chlorobenzene solvent of 5ml, reacted 2 minutes, catalyst system 45.
Catalyst system prepares the preparation of embodiment 46 catalyst system 46
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 23,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 5ml, reacted 2 minutes, catalyst system 46.
Catalyst system prepares the preparation of embodiment 47 catalyst system 47
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 24,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 5ml, reacted 2 minutes, catalyst system 47.
Catalyst system prepares the preparation of embodiment 48 catalyst system 48
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 25,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 5ml, reacted 2 minutes, catalyst system 48.
Catalyst system prepares the preparation of embodiment 49 catalyst system 49
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 25,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 10ml, reacted 2 minutes, catalyst system 49.
Catalyst system prepares the preparation of embodiment 50 catalyst system 50
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 25,5 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 5ml, reacted 2 minutes, catalyst system 50.
Catalyst system prepares the preparation of embodiment 51 catalyst system 51
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 25,20 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 5ml, reacted 2 minutes, catalyst system 51.
Catalyst system prepares the preparation of embodiment 52 catalyst system 52
Under-20 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 25,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 5ml, reacted 2 minutes, catalyst system 52.
Catalyst system prepares the preparation of embodiment 53 catalyst system 53
Under 60 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 25,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 5ml, reacted 2 minutes, catalyst system 53.
Catalyst system prepares the preparation of embodiment 54 catalyst system 54
Under 80 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 25,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 5ml, reacted 2 minutes, catalyst system 54.
Catalyst system prepares the preparation of embodiment 55 catalyst system 55
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 26,5 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 5ml, reacted 2 minutes, catalyst system 55.
Catalyst system prepares the preparation of embodiment 56 catalyst system 56
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 27,20 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the chlorobenzene solvent of 5ml, reacted 2 minutes, catalyst system 56.
Catalyst system prepares the preparation of embodiment 57 catalyst system 57
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 28,10 μ mol[Ph to 25ml 3C] { B (C 6F 5) 4] and the toluene solvant of 5ml, reacted 2 minutes, catalyst system 57.
Catalyst system prepares the preparation of embodiment 58 catalyst system 58
Under-20 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 28,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 5ml, reacted 2 minutes, catalyst system 58.
Catalyst system prepares the preparation of embodiment 59 catalyst system 59
Under 80 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 28,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the toluene solvant of 5ml, reacted 2 minutes, catalyst system 59.
Catalyst system prepares the preparation of embodiment 60 catalyst system 60
Under 25 ℃, in the polymerization bottle anhydrous, that anaerobic is handled, add 10 μ mol title complexs, 28,10 μ mol[Ph to 25ml 3C] [B (C 6F 5) 4] and the chlorobenzene solvent of 5ml, reacted 2 minutes, catalyst system 60.
Aggregated application embodiment is as follows:
Application Example 1
Catalyst system 1 with preparation embodiment 1 obtains adds 2.5mmol styrene monomer (monomer is 250: 1 with the mol ratio of title complex 1).Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 1 minute.Adding the 2ml volumetric concentration is the ethanolic soln termination polyreaction of 10% hydrochloric acid, pour reaction soln in 100ml methyl alcohol sedimentation, get polystyrene white solid powder, again this polystyrene white solid powder was placed vacuum drying oven dry 48 hours, obtain exsiccant polystyrene white solid powder, net weight 0.26g.Transformation efficiency 100%.Calculating polymerization activity is 1.56 * 10 6Gmol Sc -1h -1, with the number-average molecular weight (M of high temperature gpc analysis polystyrene n) be 6.6 ten thousand, molecular weight distribution (M w/ M n) be 1.39.Normality between the nmr analysis polystyrene (rrrr) is 100%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 271 ℃.
Application Example 2
Catalyst system 2 with preparation embodiment 2 obtains adds 10mmol styrene monomer (monomer is 1000: 1 with the mol ratio of title complex 1).Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 1 minute.Adding the 2ml volumetric concentration is the ethanolic soln termination polyreaction of 10% hydrochloric acid, pour reaction soln in 100ml methyl alcohol sedimentation, get polystyrene white solid powder, again this polystyrene white solid powder was placed vacuum drying oven dry 48 hours, obtain exsiccant polystyrene white solid powder, net weight 1.04g.Transformation efficiency 100%.Calculating polymerization activity is 6.24 * 10 6G mol Sc -1h -1, with the number-average molecular weight (M of high temperature gpc analysis polystyrene n) be 36.3 ten thousand, molecular weight distribution (M w/ M n) be 1.41.Normality between the nmr analysis polystyrene (rrrr) is 100%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 272 ℃.
Application Example 3
Catalyst system 3 with preparation embodiment 3 obtains adds 20mmol styrene monomer (monomer is 2000: 1 with the mol ratio of title complex 1).Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 1.5 minutes.Adding the 2ml volumetric concentration is the ethanolic soln termination polyreaction of 10% hydrochloric acid, pour reaction soln in 100ml methyl alcohol sedimentation, get polystyrene white solid powder, again this polystyrene white solid powder was placed vacuum drying oven dry 48 hours, obtain exsiccant polystyrene white solid powder, net weight 2.08g.Transformation efficiency 100%.Calculating polymerization activity is 8.32 * 10 6Gmol Sc -1h -1, with the number-average molecular weight (M of high temperature gpc analysis polystyrene n) be 53.6 ten thousand, molecular weight distribution (M w/ M n) be 1.33.Normality between the nmr analysis polystyrene (rrrr) is 100%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 272 ℃.
Application Example 4
Catalyst system 4 with preparation embodiment 4 obtains adds 30mmol styrene monomer (monomer is 3000: 1 with the mol ratio of title complex 1).Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 2 minutes.Adding the 2ml volumetric concentration is the ethanolic soln termination polyreaction of 10% hydrochloric acid, pour reaction soln in 100ml methyl alcohol sedimentation, get polystyrene white solid powder, again this polystyrene white solid powder was placed vacuum drying oven dry 48 hours, obtain exsiccant polystyrene white solid powder, net weight 3.12g.Transformation efficiency 100%.Calculating polymerization activity is 9.36 * 10 6G mol Sc -1h -1, with the number-average molecular weight (M of high temperature gpc analysis polystyrene n) be 86.3 ten thousand, molecular weight distribution (M w/ M n) be 1.45.Normality between the nmr analysis polystyrene (rrrr) is 100%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 270 ℃.
Application Example 5
Catalyst system 5 with preparation embodiment 5 obtains adds 40mmol styrene monomer (monomer is 4000: 1 with the mol ratio of title complex 1).Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 2 minutes.Adding the 2ml volumetric concentration is the ethanolic soln termination polyreaction of 10% hydrochloric acid, pour reaction soln in 100ml methyl alcohol sedimentation, get polystyrene white solid powder, again this polystyrene white solid powder was placed vacuum drying oven dry 48 hours, obtain exsiccant polystyrene white solid powder, net weight 4.16g.Transformation efficiency 100%.Calculating polymerization activity is 1.25 * 10 7G mol Sc -1h -1, with the number-average molecular weight (M of high temperature gpc analysis polystyrene n) be 1,000,000, molecular weight distribution (M w/ M n) be 1.40.Normality between the nmr analysis polystyrene (rrrr) is 100%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 272 ℃.
Application Example 6
Catalyst system 6 with preparation embodiment 6 obtains adds 20mmol styrene monomer (monomer is 2000: 1 with the mol ratio of title complex 1).Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 15 minutes.Adding the 2ml volumetric concentration is the ethanolic soln termination polyreaction of 10% hydrochloric acid, pour reaction soln in 100ml methyl alcohol sedimentation, get polystyrene white solid powder, again this polystyrene white solid powder was placed vacuum drying oven dry 48 hours, obtain exsiccant polystyrene white solid powder, net weight 2.08g.Transformation efficiency 100%.Calculating polymerization activity is 8.32 * 10 6Gmol Sc -1h -1, with the number-average molecular weight (M of high temperature gpc analysis polystyrene n) be 13.7 ten thousand, molecular weight distribution (M w/ M n) be 1.86.Normality between the nmr analysis polystyrene (rrrr) is 80%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 266 ℃.
Application Example 7
Catalyst system 7 with preparation embodiment 7 obtains adds 5mmol styrene monomer (monomer is 500: 1 with the mol ratio of title complex 1).Polymerization bottle places-20 ℃ of thermostatic baths, stirs reaction down 5 minutes.Adding the 2ml volumetric concentration is the ethanolic soln termination polyreaction of 10% hydrochloric acid, pour reaction soln in 100ml methyl alcohol sedimentation, get polystyrene white solid powder, again this polystyrene white solid powder was placed vacuum drying oven dry 48 hours, obtain exsiccant polystyrene white solid powder, net weight 0.52g.Transformation efficiency 100%.Calculating polymerization activity is 6.24 * 10 5G mol Sc -1h -1, with the number-average molecular weight (M of high temperature gpc analysis polystyrene n) be 20.6 ten thousand, molecular weight distribution (M w/ M n) be 1.30.Normality between the nmr analysis polystyrene (rrrr) is 100%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 270 ℃.
Application Example 8
Catalyst system 8 with preparation embodiment 8 obtains adds 10mmol styrene monomer (monomer is 1000: 1 with the mol ratio of title complex 1).Polymerization bottle places 40 ℃ of thermostatic baths, stirs reaction down 1 minute.Adding the 2ml volumetric concentration is the ethanolic soln termination polyreaction of 10% hydrochloric acid, pour reaction soln in 100ml methyl alcohol sedimentation, get polystyrene white solid powder, again this polystyrene white solid powder was placed vacuum drying oven dry 48 hours, obtain exsiccant polystyrene white solid powder, net weight 1.04g.Transformation efficiency 100%.Calculating polymerization activity is 6.24 * 10 6G mol Sc -1h -1, with the number-average molecular weight (M of high temperature gpc analysis polystyrene n) be 40.5 ten thousand, molecular weight distribution (M w/ M n) be 1.48.Normality between the nmr analysis polystyrene (rrrr) is 100%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 271 ℃.
Application Example 9
Catalyst system 9 with preparation embodiment 9 obtains adds 20mmol styrene monomer (monomer is 2000: 1 with the mol ratio of title complex 1).Polymerization bottle places 80 ℃ of thermostatic baths, stirs reaction down 1 minute.Adding the 2ml volumetric concentration is the ethanolic soln termination polyreaction of 10% hydrochloric acid, pour reaction soln in 100ml methyl alcohol sedimentation, get polystyrene white solid powder, again this polystyrene white solid powder was placed vacuum drying oven dry 48 hours, obtain exsiccant polystyrene white solid powder, net weight 2.08g.Transformation efficiency 100%.Calculating polymerization activity is 1.25 * 10 7G mol Sc -1h -1, with the number-average molecular weight (M of high temperature gpc analysis polystyrene n) be 55.7 ten thousand, molecular weight distribution (M w/ M n) be 1.57.Normality between the nmr analysis polystyrene (rrrr) is 100%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 270 ℃.
Application Example 10
Catalyst system 10 with preparation embodiment 10 obtains adds 10mmol styrene monomer (monomer is 1000: 1 with the mol ratio of title complex 2).Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 30 minutes.Adding the 2ml volumetric concentration is the ethanolic soln termination polyreaction of 10% hydrochloric acid, pour reaction soln in 100ml methyl alcohol sedimentation, get polystyrene white solid powder, again this polystyrene white solid powder was placed vacuum drying oven dry 48 hours, obtain exsiccant polystyrene white solid powder, net weight 0.83g.Transformation efficiency 80%.Calculating polymerization activity is 1.67 * 10 5Gmol Y -1h -1, with the number-average molecular weight (M of high temperature gpc analysis polystyrene n) be 18.5 ten thousand, molecular weight distribution (M w/ M n) be 1.85.Normality between the nmr analysis polystyrene (rrrr) is 93%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 268 ℃.
The step of the method for preparing syndiotactic polystyrene of Application Example 11-23 is with Application Example 1-10, and the result of condition and gained is as shown in table 2:
The application of table 2 constraint geometrical rear-earth alkyl complexes in vinylbenzene (St) syndiotactic polymerization
Application Example Catalyst system ??St/Ln Polymerization temperature (℃) Polymerization time (min) Transformation efficiency (%) Polymerization activity (gmol Ln -1h -1) Normality between polystyrene (rrrr) ??M n×10 -4 ??M w/M n ??T m(℃)
??1 ??1 ??250 ??25 ??1 ??100 ??1.56×10 6 ??100％ ??6.6 ??1.39 ??271
??2 ??2 ??1000 ??25 ??1 ??100 ??6.24×10 6 ??100％ ??36.3 ??1.41 ??272
??3 ??3 ??2000 ??25 ??1.5 ??100 ??8.32×10 6 ??100％ ??53.6 ??1.33 ??272
??4 ??4 ??3000 ??25 ??2 ??100 ??9.36×10 6 ??100％ ??86.3 ??1.45 ??270
??5 ??5 ??4000 ??25 ??2 ??100 ??1.25×10 7 ??100％ ??100 ??1.40 ??272
??6 ??6 ??2000 ??25 ??1.5 ??100 ??8.32×10 6 ??80％ ??13.7 ??1.86 ??266
??7 ??7 ??500 ??-20 ??5 ??100 ??6.24×10 5 ??100％ ??20.6 ??1.30 ??270
??8 ??8 ??1000 ??40 ??1 ??100 ??6.24×10 6 ??100％ ??40.5 ??1.48 ??271
??9 ??9 ??2000 ??80 ??1 ??100 ??1.25×10 7 ??100％ ??55.7 ??1.57 ??270
??10 ??10 ??1000 ??25 ??30 ??80 ??1.67×10 5 ??93％ ??18.5 ??1.85 ??268
??11 ??11 ??1500 ??25 ??10 ??100 ??9.36×10 5 ??100％ ??60.5 ??1.76 ??271
Application Example Catalyst system ??St/Ln Polymerization temperature (℃) Polymerization time (min) Transformation efficiency (%) Polymerization activity (gmol Ln -1h -1) Normality between polystyrene (rrrr) ??M n×10 -4 ??M w/M n ??T m(℃)
??12 ??12 ??2500 ??25 ??25 ??100 ??6.24×10 5 ??100％ ??68.3 ??1.91 ??272
??13 ??13 ??250 ??25 ??1 ??100 ??1.56×10 6 ??100％ ??7.8 ??1.89 ??271
??14 ??14 ??2000 ??25 ??3 ??100 ??4.16×10 6 ??100％ ??64.3 ??1.83 ??271
??15 ??15 ??4000 ??25 ??8 ??100 ??3.12×10 6 ??100％ ??93.4 ??1.93 ??271
??16 ??16 ??3000 ??25 ??30 ??100 ??6.24×10 5 ??100％ ??86.3 ??2.00 ??266
??17 ??17 ??2000 ??-20 ??10 ??100 ??1.25×10 6 ??100％ ??38.2 ??1.37 ??270
??18 ??18 ??2000 ??80 ??1.5 ??100 ??8.32×10 6 ??100％ ??67.2 ??1.78 ??271
??19 ??19 ??2000 ??25 ??10 ??100 ??1.25×10 6 ??100％ ??48.2 ??1.45 ??270
??20 ??20 ??2000 ??25 ??2 ??100 ??6.24×10 6 ??100％ ??52.2 ??1.88 ??271
??21 ??21 ??2000 ??25 ??20 ??100 ??6.24×10 5 ??84％ ??32.5 ??1.97 ??267
??22 ??22 ??2000 ??25 ??2 ??100 ??6.24×10 6 ??100％ ??62.3 ??1.46 ??271
Application Example Catalyst system ??St/Ln Polymerization temperature (℃) Polymerization time (min) Transformation efficiency (%) Polymerization activity (gmol Ln -1h -1) Normality between polystyrene (rrrr) ??M n×10 -4 ??M w/M n ??T m(℃)
??23 ??23 ??2000 ??25 ??2 ??100 ??6.24×10 6 ??100％ ??56.7 ??1.62 ??272
Application Example 24
Catalyst system 24 with preparation embodiment 24 obtains adds 2.5mmol styrene monomer (monomer is 250: 1 with the mol ratio of title complex 13).Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 1 minute.Adding the 2ml volumetric concentration is the ethanolic soln termination polyreaction of 10% hydrochloric acid, pour reaction soln in 100ml methyl alcohol sedimentation, get polystyrene white solid powder, again this polystyrene white solid powder was placed vacuum drying oven dry 48 hours, obtain exsiccant polystyrene white solid powder, net weight 0.26g.Transformation efficiency 100%.Calculating polymerization activity is 1.56 * 10 6Gmol Sc -1h -1, with the number-average molecular weight (M of high temperature gpc analysis polystyrene n) be 760,000, molecular weight distribution (M w/ M n) be 1.37.Normality between the nmr analysis polystyrene (rrrr) is 100%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 271 ℃.
Application Example 25
Catalyst system 25 with preparation embodiment 25 obtains adds 10mmol styrene monomer (monomer is 1000: 1 with the mol ratio of title complex 13).Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 1 minute.Adding the 2ml volumetric concentration is the ethanolic soln termination polyreaction of 10% hydrochloric acid, pour reaction soln in 100ml methyl alcohol sedimentation, get polystyrene white solid powder, again this polystyrene white solid powder was placed vacuum drying oven dry 48 hours, obtain exsiccant polystyrene white solid powder, net weight 1.04g.Transformation efficiency 100%.Calculating polymerization activity is 6.24 * 10 6Gmol Sc -1h -1, with the number-average molecular weight (M of high temperature gpc analysis polystyrene n) be 42.4 ten thousand, molecular weight distribution (M w/ M n) be 1.48.Normality between the nmr analysis polystyrene (rrrr) is 100%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 270 ℃.
Application Example 26
Catalyst system 26 with preparation embodiment 26 obtains adds 20mmol styrene monomer (monomer is 2000: 1 with the mol ratio of title complex 13).Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 1.5 minutes.Adding the 2ml volumetric concentration is the ethanolic soln termination polyreaction of 10% hydrochloric acid, pour reaction soln in 100ml methyl alcohol sedimentation, get polystyrene white solid powder, again this polystyrene white solid powder was placed vacuum drying oven dry 48 hours, obtain exsiccant polystyrene white solid powder, net weight 2.08g.Transformation efficiency 100%.Calculating polymerization activity is 8.32 * 10 6Gmol Sc -1h -1, with the number-average molecular weight (M of high temperature gpc analysis polystyrene n) be 57.6 ten thousand, molecular weight distribution (M w/ M n) be 1.43.Normality between the nmr analysis polystyrene (rrrr) is 100%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 272 ℃.
Application Example 27
Catalyst system 27 with preparation embodiment 27 obtains adds 30mmol styrene monomer (monomer is 3000: 1 with the mol ratio of title complex 13).Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 2 minutes.Adding the 2ml volumetric concentration is the ethanolic soln termination polyreaction of 10% hydrochloric acid, pour reaction soln in 100ml methyl alcohol sedimentation, get polystyrene white solid powder, again this polystyrene white solid powder was placed vacuum drying oven dry 48 hours, obtain exsiccant polystyrene white solid powder, net weight 3.12g.Transformation efficiency 100%.Calculating polymerization activity is 9.36 * 10 6Gmol Sc -1h -1, with the number-average molecular weight (M of high temperature gpc analysis polystyrene n) be 80.7 ten thousand, molecular weight distribution (M w/ M n) be 1.49.Normality between the nmr analysis polystyrene (rrrr) is 100%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 271 ℃.
Application Example 28
Catalyst system 28 with preparation embodiment 28 obtains adds 40mmol styrene monomer (monomer is 4000: 1 with the mol ratio of title complex 13).Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 2 minutes.Adding the 2ml volumetric concentration is the ethanolic soln termination polyreaction of 10% hydrochloric acid, pour reaction soln in 100ml methyl alcohol sedimentation, get polystyrene white solid powder, again this polystyrene white solid powder was placed vacuum drying oven dry 48 hours, obtain exsiccant polystyrene white solid powder, net weight 4.16g.Transformation efficiency 100%.Calculating polymerization activity is 1.25 * 10 7Gmol Sc -1h -1, with the number-average molecular weight (M of high temperature gpc analysis polystyrene n) be 98.7 ten thousand, molecular weight distribution (M w/ M n) be 1.54.Normality between the nmr analysis polystyrene (rrrr) is 100%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 272 ℃.
Application Example 29
Catalyst system 29 with preparation embodiment 29 obtains adds 20mmol styrene monomer (monomer is 2000: 1 with the mol ratio of title complex 13).Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 1.5 minutes.Adding the 2ml volumetric concentration is the ethanolic soln termination polyreaction of 10% hydrochloric acid, pour reaction soln in 100ml methyl alcohol sedimentation, get polystyrene white solid powder, again this polystyrene white solid powder was placed vacuum drying oven dry 48 hours, obtain exsiccant polystyrene white solid powder, net weight 2.08g.Transformation efficiency 100%.Calculating polymerization activity is 8.32 * 10 6Gmol Sc -1h -1, with the number-average molecular weight (M of high temperature gpc analysis polystyrene n) be 23.7 ten thousand, molecular weight distribution (M w/ M n) be 1.95.Normality between the nmr analysis polystyrene (rrrr) is 89%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 267 ℃.
Application Example 30
Catalyst system 30 with preparation embodiment 30 obtains adds 5mmol styrene monomer (monomer is 500: 1 with the mol ratio of title complex 13).Polymerization bottle places-20 ℃ of thermostatic baths, stirs reaction down 5 minutes.Adding the 2ml volumetric concentration is the ethanolic soln termination polyreaction of 10% hydrochloric acid, pour reaction soln in 100ml methyl alcohol sedimentation, get polystyrene white solid powder, again this polystyrene white solid powder was placed vacuum drying oven dry 48 hours, obtain exsiccant polystyrene white solid powder, net weight 0.52g.Transformation efficiency 100%.Calculating polymerization activity is 6.24 * 10 5Gmol Sc -1h -1, with the number-average molecular weight (M of high temperature gpc analysis polystyrene n) be 31.2 ten thousand, molecular weight distribution (M w/ M n) be 1.43.Normality between the nmr analysis polystyrene (rrrr) is 100%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 270 ℃.
Application Example 31
Catalyst system 31 with preparation embodiment 31 obtains adds 10mmol styrene monomer (monomer is 1000: 1 with the mol ratio of title complex 13).Polymerization bottle places 40 ℃ of thermostatic baths, stirs reaction down 1 minute.Adding the 2ml volumetric concentration is the ethanolic soln termination polyreaction of 10% hydrochloric acid, pour reaction soln in 100ml methyl alcohol sedimentation, get polystyrene white solid powder, again this polystyrene white solid powder was placed vacuum drying oven dry 48 hours, obtain exsiccant polystyrene white solid powder, net weight 1.04g.Transformation efficiency 100%.Calculating polymerization activity is 6.24 * 10 6Gmol Sc -1h -1, with the number-average molecular weight (M of high temperature gpc analysis polystyrene n) be 48.5 ten thousand, molecular weight distribution (M w/ M n) be 1.56.Normality between the nmr analysis polystyrene (rrrr) is 100%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 272 ℃.
Application Example 32
Catalyst system 32 with preparation embodiment 32 obtains adds 20mmol styrene monomer (monomer is 2000: 1 with the mol ratio of title complex 13).Polymerization bottle places 80 ℃ of thermostatic baths, stirs reaction down 1 minute.Adding the 2ml volumetric concentration is the ethanolic soln termination polyreaction of 10% hydrochloric acid, pour reaction soln in 100ml methyl alcohol sedimentation, get polystyrene white solid powder, again this polystyrene white solid powder was placed vacuum drying oven dry 48 hours, obtain exsiccant polystyrene white solid powder, net weight 2.08g.Transformation efficiency 100%.Calculating polymerization activity is 1.25 * 10 7Gmol Sc -1h -1, with the number-average molecular weight (M of high temperature gpc analysis polystyrene n) be 58.7 ten thousand, molecular weight distribution (M w/ M n) be 1.65.Normality between the nmr analysis polystyrene (rrrr) is 100%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 270 ℃.
Application Example 33
Catalyst system 33 with preparation embodiment 33 obtains adds 5mmol styrene monomer (monomer is 500: 1 with the mol ratio of title complex 14).Polymerization bottle places 25 ℃ of thermostatic baths, stirs reaction down 15 minutes.Adding the 2ml volumetric concentration is the ethanolic soln termination polyreaction of 10% hydrochloric acid, pour reaction soln in 100ml methyl alcohol sedimentation, get polystyrene white solid powder, again this polystyrene white solid powder was placed vacuum drying oven dry 48 hours, obtain exsiccant polystyrene white solid powder, net weight 0.41g.Transformation efficiency 80%.Calculating polymerization activity is 1.66 * 10 5G mol Y -1h -1, with the number-average molecular weight (M of high temperature gpc analysis polystyrene n) be 4.6 ten thousand, molecular weight distribution (M w/ M n) be 1.90.Normality between the nmr analysis polystyrene (rrrr) is 80%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 266 ℃.
The step of the method for preparing syndiotactic polystyrene of Application Example 34-60 is with Application Example 24-33, and the result of condition and gained is as shown in table 3:
The application of table 3 rare earth allyl complex with constrained geometry configuration in vinylbenzene (St) syndiotactic polymerization
Application Example Catalyst system ??St/Ln Polymerization temperature (℃) Polymerization time (min) Transformation efficiency (%) Polymerization activity (g mol Ln -1h -1) Normality between polystyrene (rrrr) ??M n×10 -4 ??M w/M n ??T m(℃)
??24 ??24 ??250 ??25 ??1 ??100 ??1.56×10 6 ??100％ ??7.6 ??1.37 ??271
??25 ??25 ??1000 ??25 ??1 ??100 ??6.24×10 6 ??100％ ??42.4 ??1.48 ??270
??26 ??26 ??2000 ??25 ??1.5 ??100 ??8.32×10 6 ??100％ ??57.6 ??1.43 ??272
??27 ??27 ??3000 ??25 ??2 ??100 ??9.36×10 6 ??100％ ??80.7 ??1.49 ??271
??28 ??28 ??4000 ??25 ??2 ??100 ??1.25×10 7 ??100％ ??98.7 ??1.54 ??272
??29 ??29 ??2000 ??25 ??1.5 ??100 ??8.32×10 6 ??89％ ??23.7 ??1.95 ??267
??30 ??30 ??500 ??-20 ??5 ??100 ??6.24×10 5 ??100％ ??31.2 ??1.43 ??270
??31 ??31 ??1000 ??40 ??1 ??100 ??6.24×10 6 ??100％ ??48.5 ??1.56 ??272
??32 ??32 ??2000 ??80 ??1 ??100 ??1.25×10 7 ??100％ ??58.7 ??1.65 ??272
??33 ??33 ??500 ??25 ??15 ??80 ??1.66×10 5 ??80％ ??4.6 ??1.90 ??266
??34 ??34 ??1500 ??25 ??10 ??100 ??9.36×10 5 ??100％ ??67.5 ??1.82 ??271
??35 ??35 ??2500 ??25 ??25 ??100 ??6.24×10 5 ??100％ ??70.3 ??1.98 ??272
??36 ??36 ??250 ??25 ??1 ??100 ??1.56×10 6 ??100％ ??5.3 ??1.97 ??270
Application Example Catalyst system ??St/Ln Polymerization temperature (℃) Polymerization time (min) Transformation efficiency (%) Polymerization activity (g mol Ln -1h -1) Normality between polystyrene (rrrr) ??M n×10 -4 ??M w/M n ??T m(℃)
??37 ??37 ??500 ??25 ??1 ??100 ??3.12×10 6 ??100％ ??9.7 ??1.94 ??270
????38 ??38 750 25 ??1 ????100 ????4.68×10 6 ????100％ ??15.3 ??1.98 ??271
????39 ??39 1000 25 ??1 ????100 ????6.24×10 6 ????100％ ??22.3 ??1.88 ??270
????40 ??40 4000 25 ??2 ????100 ????1.25×10 7 ????100％ ??90.5 ??1.93 ??272
????41 ??41 1000 -20 ??20 ????100 ????3.12×10 5 ????100％ ??34.5 ??1.67 ??271
????42 ??42 1000 80 ??1 ????100 ????6.24×10 6 ????100％ ??44.3 ??1.78 ??270
????43 ??43 2000 25 ??1 ????100 ????1.25×10 7 ????100％ ??42.7 ??1.43 ??272
????44 ??44 2000 25 ??2 ????100 ????6.24×10 6 ????100％ ??56.3 ??1.53 ??270
????45 ??45 2000 25 ??10 ????100 ????1.25×10 6 ????80％ ??19.6 ??1.87 ??266
????46 ??46 1500 25 ??2 ????100 ????4.68×10 6 ????100％ ??44.2 ??1.42 ??270
????47 ??47 1500 25 ??2 ????100 ????4.68×10 6 ????100％ ??53.8 ??1.46 ??272
????48 ??48 2000 25 ??1 ????100 ????1.25×10 7 ????100％ ??48.3 ??1.38 ??270
????49 ??49 4000 25 ??2 ????100 ????1.25×10 7 ????100％ ??98.8 ??1.42 ??272
Application Example Catalyst system ??St/Ln Polymerization temperature (℃) Polymerization time (min) Transformation efficiency (%) Polymerization activity (g mol Ln -1h -1) Normality between polystyrene (rrrr) ??M n×10 -4 ??M w/M n ??T m(℃)
????50 ??50 2000 25 ??1 ????100 ????1.25×10 7 ????100％ ??89.5 ??1.45 ??270
????51 ??51 2000 25 ??1 ????100 ????1.25×10 7 ????100％ ??56.1 ??1.43 ??272
????52 ??52 2000 -20 ??20 ????100 ????6.25×10 5 ????100％o ??60.2 ??1.32 ??270
????53 ??53 2000 60 ??1 ????100 ????1.25×10 7 ????100％ ??36.5 ??1.53 ??271
????54 ??54 2000 80 ??1 ????100 ????1.25×10 7 ????100％o ??34.8 ??1.62 ??270
????55 ??55 1500 25 ??1 ????100 ????9.36×10 6 ????100％ ??61.7 ??1.48 ??270
????56 ??56 1500 25 ??1 ????100 ????9.36×10 6 ????90％ ??23.4 ??1.78 ??269
????57 ??57 2000 25 ??1 ????100 ????1.25×10 7 ????100％ ??43.6 ??1.57 ??270
????58 ??58 2000 -20 ??10 ????100 ????1.25×10 6 ????100％ ??34.8 ??1.49 ??272
????59 ??59 2000 80 ??1 ????100 ????1.25×10 7 ????100％ ??34.8 ??1.67 ??270
????60 ??60 1500 25 ??1 ????100 ????9.36×10 6 ????85％ ??35.6 ??1.97 ??268
Can draw from aggregated application embodiment 1-60, described constraint geometrical rear-earth title complex all can be realized cinnamic high reactivity (1.66 * 10 5G mol Ln -1h -1～1.25 * 10 7G mol Ln -1h -1), rule (80%～100%) polymerization between height.Prepared polystyrene number-average molecular weight in 4.6～1,000,000 scopes, molecular weight distribution narrower (1.30～1.98), fusing point is in 266～272 ℃ of scopes.Catalyst system has higher adaptability to temperature, and in-20～80 ℃ polymerization temperature scope, the Gao Junke of normality between polystyrene (rrrr) reaches 100%.

Claims (14)

1. the constraint geometrical rear-earth title complex is characterized in that molecular formula is [R 1-(3-R 2-4-R 3-5-R 4-6-R 5) C 5N] LnX 2, structural formula is:
Figure FSA00000052886800011
R in the formula 1Be cyclopentadienyl derivative C 5A 4, indenyl derivative C 9A 6Or fluorenyl derivative C 13A 8A is the substituting group of cyclopentadienyl, the substituting group of indenyl or the substituting group on the fluorenyl, and A is identical or different, and A is selected from hydrogen, aliphatic hydrocarbyl or aromatic hydrocarbyl; R 2Be the substituting group on the skeleton pyridine ring, be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl or phenyl; R 3Be the substituting group on the skeleton pyridine ring, be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl or phenyl; R 4Be the substituting group on the skeleton pyridine ring, be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl or phenyl; R 5Be the substituting group on the skeleton pyridine ring, be selected from hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl, phenyl, 2,6-3,5-dimethylphenyl, 4-aminomethyl phenyl, mesitylene base, 2,6-diisopropyl phenyl, 2,4,6-triisopropyl phenyl or 2,6-di-tert-butyl-phenyl; Ln represents rare earth metal, is selected from Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu; X is a single anion ligand, is selected from CH 2SiMe 3, CH (SiMe 3) 2, 1,3-C 3H 5, 1,3-C 3H 4(Me) or 1,3-C 3H 3(SiMe 3) 2
2. constraint geometrical rear-earth title complex as claimed in claim 1 is characterized in that, described R 1Be tetramethyl-ring pentadienyl or indenyl.
3. constraint geometrical rear-earth title complex as claimed in claim 1 is characterized in that, described R 2Be hydrogen or methyl.
4. constraint geometrical rear-earth title complex as claimed in claim 1 is characterized in that, described R 3Be hydrogen.
5. constraint geometrical rear-earth title complex as claimed in claim 1 is characterized in that, described R 4Be hydrogen.
6. constraint geometrical rear-earth title complex as claimed in claim 1 is characterized in that, described R 5Be hydrogen, methyl, phenyl, 2,6-3,5-dimethylphenyl or 2,4,6-triisopropyl phenyl.
7. constraint geometrical rear-earth title complex as claimed in claim 1 is characterized in that, described Ln is Sc, Y, Nd, Gd or Lu.
8. constraint geometrical rear-earth title complex as claimed in claim 1 is characterized in that, described X is CH 2SiMe 3Or 1,3-C 3H 5
9. constraint geometrical rear-earth title complex as claimed in claim 1 is characterized in that, it is in following 1～28 the title complex any one, wherein:
Title complex 1:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=H, Ln=Sc, X=CH 2SiMe 3
Title complex 2:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=H, Ln=Y, X=CH 2SiMe 3
Title complex 3:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=H, Ln=Nd, X=CH 2SiMe 3
Title complex 4:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=H, Ln=Gd, X=CH 2SiMe 3
Title complex 5:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=H, Ln=Lu, X=CH 2SiMe 3
Title complex 6:R 1=C 5Me 4, R 2=Me, R 3=H, R 4=H, R 5=H, Ln=Sc, X=CH 2SiMe 3
Title complex 7:R 1=C 5Me 4, R 2=Me, R 3=H, R 4=H, R 5=H, Ln=Lu, X=CH 2SiMe 3
Title complex 8:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=Me, Ln=Sc, X=CH 2SiMe 3
Title complex 9:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=Me, Ln=Lu, X=CH 2SiMe 3
Title complex 10:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=2,4,6-(iPr) 3C 6H 2, Ln=Sc, X=CH 2SiMe 3
Title complex 11:R 1=C 9H 6, R 2=H, R 3=H, R 4=H, R 5=H, Ln=Sc, X=CH 2SiMe 3
Title complex 12:R 1=C 9H 6, R 2=H, R 3=H, R 4=H, R 5=2,4,6-(iPr) 3C 6H 2, Ln=Sc, X=CH 2SiMe 3,
Title complex 13:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=H, Ln=Sc, X=1,3-C 3H 5
Title complex 14:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=H, Ln=Y, X=1,3-C 3H 5
Title complex 15:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=H, Ln=Nd, X=1,3-C 3H 5
Title complex 16:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=H, Ln=Gd, X=1,3-C 3H 5
Title complex 17:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=H, Ln=Lu, X=1,3-C 3H 5
Title complex 18:R 1=C 5Me 4, R 2=Me, R 3=H, R 4=H, R 5=H, Ln=Sc, X=1,3-C 3H 5
Title complex 19:R 1=C 5Me 4, R 2=Me, R 3=H, R 4=H, R 5=H, Ln=Lu, X=1,3-C 3H 5
Title complex 20:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=Me, Ln=Sc, X=1,3-C 3H 5
Title complex 21:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=Me, Ln=Lu, X=1,3-C 3H 5
Title complex 22:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=C 6H 5, Ln=Sc, X=1,3-C 3H 5
Title complex 23:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=2,6-(Me) 2C 6H 3, Ln=Sc, X=1,3-C 3H 5
Title complex 24:R 1=C 5Me 4, R 2=H, R 3=H, R 4=H, R 5=2,4,6-(iPr) 3C 6H 2, Ln=Sc, X=1,3-C 3H 5
Title complex 25:R 1=C 9H 6, R 2=H, R 3=H, R 4=H, R 5=H, Ln=Sc, X=1,3-C 3H 5
Title complex 26:R 1=C 9H 6, R 2=H, R 3=H, R 4=H, R 5=H, Ln=Lu, X=1,3-C 3H 5
Title complex 27:R 1=C 9H 6, R 2=H, R 3=H, R 4=H, R 5=2,4,6-(iPr) 3C 6H 2, Ln=Sc, X=1,3-C 3H 5
Title complex 28:R 1=C 9H 6, R 2=H, R 3=H, R 4=H, R 5=2,4,6-(iPr) 3C 6H 2, Ln=Lu, X=1,3-C 3H 5
10. the method for making of constraint geometrical rear-earth title complex as claimed in claim 1 comprises: the method for making of (1) constraint geometrical rear-earth alkyl complexes; (2) method for making of rare earth allyl complex with constrained geometry configuration; It is characterized in that condition and step are as follows:
(1) condition of the method for making of constraint geometrical rear-earth alkyl complexes and step are as follows: at N 2Under the protection, constrained geometry configuration part R 1H-(3-R 2-4-R 3-5-R 4-6-R 5) C 5N is dissolved in tetrahydrofuran (THF) and places-78～0 ℃, the concentration of 1 times of amount that adds the mol of described constrained geometry configuration part is the hexane solution of 1.0～2.0mol/L n-Butyl Lithium, react after 1 hour, the rare earth trichloride of 1 times of amount that adds the mol of described constrained geometry configuration part, react after 4 hours, add the LiCH of 2 times of amounts of the mol of described constrained geometry configuration part 2SiMe 3, room temperature reaction removed and desolvates after 4 hours, used hexane extraction, concentrated hexane, obtained the constraint geometrical rear-earth alkyl complexes; The chemical formula of described rare earth trichloride is to be LnCl 3, wherein Ln is with the Ln in the described constraint geometrical rear-earth title complex of claim 1;
(2) condition of the method for making of rare earth allyl complex with constrained geometry configuration and step are as follows: at N 2Under the protection, constrained geometry configuration part R 1H-(3-R 2-4-R 3-5-R 4-6-R 5) C 5N is dissolved in tetrahydrofuran (THF) and places-78～0 ℃, the concentration of 1 times of amount that adds the mol of described constrained geometry configuration part is the hexane solution of 1.0～2.0mol/L n-Butyl Lithium, react after 1 hour, the rare earth trichloride of 1 times of amount that adds the mol of described constrained geometry configuration part, react after 4 hours, add the C of 2 times of amounts of the mol of described constrained geometry configuration part 3H 5MgCl, room temperature reaction removed and desolvate after 12 hours, with the toluene extraction, concentrated toluene, obtained rare earth allyl complex with constrained geometry configuration; The chemical formula of described rare earth chloride is to be LnCl 3, wherein Ln is with the Ln in the described constraint geometrical rear-earth title complex of claim 1.
11. the application of constraint geometrical rear-earth title complex as claimed in claim 1 is characterized in that, the constraint geometrical rear-earth title complex is used for the catalyst system of syndiotactic polymerization of phenylethylene; This catalyst system was made up of than 2: 1～1: 2 by mol constraint geometrical rear-earth title complex and organic boron salt two components;
Described organic boron salt is: [Ph 3C] [B (C 6F 5) 4], [PhNMe 2H] [BPh 4], [PhNMe 2H] [B (C 6F 5) 4] or B (C 6F 5) 3
12. the application of constraint geometrical rear-earth title complex as claimed in claim 11 is characterized in that, the described organic boron salt that is used for the catalyst system of syndiotactic polymerization of phenylethylene is [Ph 3C] [B (C 6F 5) 4].
13. the method for making that is used for the catalyst system of syndiotactic polymerization of phenylethylene as claimed in claim 11 is characterized in that step and condition are as follows: with molecular formula is [R 1-(3-R 2-4-R 3-5-R 4-6-R 5) C 5N] LnX 2The constraint geometrical rear-earth title complex and be organic boron salt of 0.5～2 times of mol amount of selected constraint geometrical rear-earth title complex, by proportioning at C 6～C 7Aromatic hydrocarbon solvent in mix, obtain the catalyst system that homogeneous is used for syndiotactic polymerization of phenylethylene.
14. the usage that is used for the catalyst system of syndiotactic polymerization of phenylethylene as claimed in claim 11 is characterized in that step and condition are as follows:
Get the toluene or the chlorobenzene solution that are used for the catalyst system of syndiotactic polymerization of phenylethylene by described, place the reactor of handling through anhydrous, anaerobic, to count ratio be 100: 1～1000: 1 to the mol of constraint geometrical rear-earth title complex in the volume L of described solvent and the described catalyst system; Add styrene monomer, the mol ratio of the constraint geometrical rear-earth title complex in styrene monomer and the described catalyst system is 250: 1～4000: 1, and polyreaction was carried out under-20～80 ℃ 1～30 minute.The adding volumetric concentration is 10% ethanol solution hydrochloride termination polyreaction, pour reaction soln in methyl alcohol sedimentation, get polystyrene white solid powder, again this polystyrene white solid powder is placed vacuum drying oven dry, obtain exsiccant polystyrene white solid powder.
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