CN101880295B - 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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CN101880295B
CN101880295B CN2010101226577A CN201010122657A CN101880295B CN 101880295 B CN101880295 B CN 101880295B CN 2010101226577 A CN2010101226577 A CN 2010101226577A CN 201010122657 A CN201010122657 A CN 201010122657A CN 101880295 B CN101880295 B CN 101880295B
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CN101880295A (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 acatalytic 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 is1.30.

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 PS mainly realized through radical polymerization, anionoid polymerization, cationoid polymerisation and Ziegler-Natta catalyst catalyzed polymerization.According to the difference of steric configuration, PS can be divided into random polystyrene, syndiotactic polystyrene and isotactic polyphenylacetylene.Traditional radical polymerization, anionoid polymerization and cationoid polymerisation mainly obtain random polystyrene, and Ziegler-Natta catalyst is polymerizing styrene catalyzed mainly to obtain isotactic polyphenylacetylene, and high syndiotactic polystyrene was just realized (N.Ishihara by Japanese Idemitsu Kosan company through 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 owing to its superior character, and for example HMP, high crystalline, high elastic coefficient, low-k, low loss factors and good heat-resisting anti-solvent have become a kind of material that haves a great attraction in industry.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 catalystsystem; And applied for a series of patents, major cause is the titanium complex catalystsystem, like 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, report is seldom only arranged for the polymerizing styrene catalyzed appearance 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 PS 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, and normality between the PS 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 ability double-component catalyst vinylbenzene, polymerization activity is up to 1.36 * 10 7Gmol Ln -1h -1, normality between the PS 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 ability (F.Jaroschik, T.Shima, X.Li under the promotor effect; 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 ability under the effect of organic boron salt promotor of constrained geometry configuration part does not also appear in the newspapers.
Summary of the invention
One of the object of the 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 moiety, 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 limitations geometrical rear-earth title complex is any 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 the object of the 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; Introduce as follows respectively:
(1) method for making of constraint geometrical rear-earth alkyl complexes:
Synthetic route is following:
Figure GSA00000052886900041
Condition and step are following: 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 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; Add the rare earth trichloride of 1 times of amount of 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 following:
Figure GSA00000052886900042
Condition and step are following: 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 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; Add the rare earth trichloride of 1 times of amount of 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, used extracted in toluene, 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 the object of the 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 catalystsystem of syndiotactic polymerization of phenylethylene; This catalystsystem 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 preparing method's of the described catalystsystem that is used for syndiotactic polymerization of phenylethylene step and condition are following:
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 the constraint geometrical rear-earth title complex selected for use, by proportioning at C 6～C 7Aromatic hydrocarbon solvent in mix, obtain the catalystsystem of homogeneous syndiotactic polymerization of phenylethylene.
The described catalystsystem that is used for syndiotactic polymerization of phenylethylene, the step and the condition of method that is used to prepare syndiotactic polystyrene is following:
Get the toluene or the chlorobenzene solution that are used for the catalystsystem of syndiotactic polymerization of phenylethylene by described; Place the reactor drum 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 catalystsystem; Add styrene monomer, the mol ratio of the constraint geometrical rear-earth title complex in styrene monomer and the described catalystsystem 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 PS white solid powder, place vacuum drying oven dry in this PS white solid powder again, obtain exsiccant PS white solid powder.
The number-average molecular weight of the syndiotactic polystyrene of above-mentioned gained and MWD are measured with high-temperature gel permeation chromatography appearance (GPC), and fusing point is measured with DSC, normality between PS (rrrr) with 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 catalystsystem that itself and organic boron salt are formed has the characteristic 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 PS, and fusing point is in 266～272 ℃ of scopes, and number-average molecular weight is in 4.6～1,000,000 scopes, and MWD is minimum to reach 1.30.
Embodiment
It is following 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 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 is used hexane extraction, and concentrated hexane solution obtains 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
Figure GSA00000052886900062
Under-40 ℃ of conditions, be that (0.8mL 1.2mmol) is added drop-wise to 1-[2-(3-methyl) pyridyl]-2,3,4, and (0.26g is in the solution of THF 1.2mmol) (20mL) for 5-tetramethyl-ring pentadiene for the hexane solution of the n-Butyl Lithium of 1.5mol/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 is used hexane extraction, and concentrated hexane solution obtains 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, be that (0.8mL 1.2mmol) is added drop-wise to 1-[2-(3-methyl) pyridyl]-2,3,4, and (0.26g is in the solution of THF 1.2mmol) (20mL) for 5-tetramethyl-ring pentadiene for the hexane solution of the n-Butyl Lithium of 1.5mol/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 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 is used hexane extraction, and concentrated hexane solution obtains 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, be that (0.8mL 1.2mmol) is added drop-wise to 1-[2-(6-methyl) pyridyl]-2,3,4, and (0.26g is in the solution of THF 1.2mmol) (20mL) for 5-tetramethyl-ring pentadiene for the hexane solution of the n-Butyl Lithium of 1.5mol/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 is used hexane extraction, and concentrated hexane solution obtains 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
Under-40 ℃ of conditions, be that (0.8mL 1.2mmol) is added drop-wise to 1-[2-(6-methyl) pyridyl]-2,3,4, and (0.26g is in the solution of THF 1.2mmol) (20mL) for 5-tetramethyl-ring pentadiene for the hexane solution of the n-Butyl Lithium of 1.5mol/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 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 is used hexane extraction, and concentrated hexane solution obtains 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
Figure GSA00000052886900082
Under-40 ℃ of conditions, with concentration be the n-Butyl Lithium of 1.5mol/L hexane solution (0.8mL, [6-(2 1.2mmol) to be added drop-wise to 1-{2-; 4,6-triisopropyl phenyl)] pyridyl-2,3; 4, (0.48g is in the solution of 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 is used hexane extraction, and concentrated hexane solution obtains 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
Figure GSA00000052886900083
Under-20 ℃ of conditions, be that (0.6mL, (0.23g is in the solution of 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 is used hexane extraction, and concentrated hexane solution obtains 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 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 is used hexane extraction, and concentrated hexane solution obtains 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
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 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 is used extracted in 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 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 is used extracted in 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
Figure GSA00000052886900102
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 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 is used extracted in 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 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 is used extracted in 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 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 is used extracted in 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, be that (0.8mL 1.2mmol) is added drop-wise to 1-[2-(3-methyl) pyridyl]-2,3,4, and (0.26g is in the solution of THF 1.2mmol) (20mL) for 5-tetramethyl-ring pentadiene for the hexane solution of the n-Butyl Lithium of 1.5mol/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 is used extracted in 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
Under-40 ℃ of conditions, be that (0.8mL 1.2mmol) is added drop-wise to 1-[2-(3-methyl) pyridyl]-2,3,4, and (0.26g is in the solution of THF 1.2mmol) (20mL) for 5-tetramethyl-ring pentadiene for the hexane solution of the n-Butyl Lithium of 1.5mol/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 is used extracted in 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, be that (0.8mL 1.2mmol) is added drop-wise to 1-[2-(6-methyl) pyridyl]-2,3,4, and (0.26g is in the solution of THF 1.2mmol) (20mL) for 5-tetramethyl-ring pentadiene for the hexane solution of the n-Butyl Lithium of 1.5mol/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 is used extracted in 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, be that (0.8mL 1.2mmol) is added drop-wise to 1-[2-(6-methyl) pyridyl]-2,3,4, and (0.26g is in the solution of THF 1.2mmol) (20mL) for 5-tetramethyl-ring pentadiene for the hexane solution of the n-Butyl Lithium of 1.5mol/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 is used extracted in 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, be that (0.8mL 1.2mmol) is added drop-wise to 1-[2-(6-phenyl) pyridyl]-2,3,4, and (0.33g is in the solution of THF 1.2mmol) (20mL) for 5-tetramethyl-ring pentadiene for the hexane solution of the n-Butyl Lithium of 15mol/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 is used extracted in 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, with concentration be the n-Butyl Lithium of 1.5mol/L hexane solution (0.8mL, [6-(2 1.2mmol) to be added drop-wise to 1-{2-; The 6-3,5-dimethylphenyl)] pyridyl }-2,3,4; (0.36g is in the solution of 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 is used extracted in 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, with concentration be the n-Butyl Lithium of 1.5mol/L hexane solution (0.8mL, [6-(2 1.2mmol) to be added drop-wise to 1-{2-; 4,6-triisopropyl phenyl)] pyridyl-2,3; 4, (0.48g is in the solution of 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 is used extracted in 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 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 is used extracted in 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
Figure GSA00000052886900151
Under 0 ℃ of condition, be that (0.6mL, (0.23g is in the solution of 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 is used extracted in 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
Figure GSA00000052886900152
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 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 is used extracted in 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 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 is used extracted in 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 catalystsystem is following:
Catalystsystem prepares the preparation of embodiment 1 catalystsystem 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, catalystsystem 1.
Catalystsystem prepares the preparation of embodiment 2 catalystsystem 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, catalystsystem 2.
Catalystsystem prepares the preparation of embodiment 3 catalystsystem 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, catalystsystem 3.
Catalystsystem prepares the preparation of embodiment 4 catalystsystem 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, catalystsystem 4.
Catalystsystem prepares the preparation of embodiment 5 catalystsystem 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, catalystsystem 5.
Catalystsystem prepares the preparation of embodiment 6 catalystsystem 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, catalystsystem 6.
Catalystsystem prepares the preparation of embodiment 7 catalystsystem 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, catalystsystem 7.
Catalystsystem prepares the preparation of embodiment 8 catalystsystem 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, catalystsystem 8.
Catalystsystem prepares the preparation of embodiment 9 catalystsystem 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, catalystsystem 9.
Catalystsystem prepares the preparation of embodiment 10 catalystsystem 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, catalystsystem 10.
Catalystsystem prepares the preparation of embodiment 11 catalystsystem 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, catalystsystem 11.
Catalystsystem prepares the preparation of embodiment 12 catalystsystem 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, catalystsystem 12.
Catalystsystem prepares the preparation of embodiment 13 catalystsystem 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, catalystsystem 13.
Catalystsystem prepares the preparation of embodiment 14 catalystsystem 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, catalystsystem 14.
Catalystsystem prepares the preparation of embodiment 15 catalystsystem 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, catalystsystem 15.
Catalystsystem prepares the preparation of embodiment 16 catalystsystem 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, catalystsystem 16.
Catalystsystem prepares the preparation of embodiment 17 catalystsystem 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, catalystsystem 17.
Catalystsystem prepares the preparation of embodiment 18 catalystsystem 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, catalystsystem 18.
Catalystsystem prepares the preparation of embodiment 19 catalystsystem 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, catalystsystem 19.
Catalystsystem prepares the preparation of embodiment 20 catalystsystem 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, catalystsystem 20.
Catalystsystem prepares the preparation of embodiment 21 catalystsystem 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, catalystsystem 21.
Catalystsystem prepares the preparation of embodiment 22 catalystsystem 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, catalystsystem 22.
Catalystsystem prepares the preparation of embodiment 23 catalystsystem 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, catalystsystem 23.
Catalystsystem prepares the preparation of embodiment 24 catalystsystem 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, catalystsystem 24.
Catalystsystem prepares the preparation of embodiment 25 catalystsystem 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, catalystsystem 25.
Catalystsystem prepares the preparation of embodiment 26 catalystsystem 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, catalystsystem 26.
Catalystsystem prepares the preparation of embodiment 27 catalystsystem 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, catalystsystem 27.
Catalystsystem prepares the preparation of embodiment 28 catalystsystem 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, catalystsystem 28.
Catalystsystem prepares the preparation of embodiment 29 catalystsystem 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, catalystsystem 29.
Catalystsystem prepares the preparation of embodiment 30 catalystsystem 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, catalystsystem 30.
Catalystsystem prepares the preparation of embodiment 31 catalystsystem 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, catalystsystem 31.
Catalystsystem prepares the preparation of embodiment 32 catalystsystem 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, catalystsystem 32.
Catalystsystem prepares the preparation of embodiment 33 catalystsystem 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, catalystsystem 33.
Catalystsystem prepares the preparation of embodiment 34 catalystsystem 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, catalystsystem 34.
Catalystsystem prepares the preparation of embodiment 35 catalystsystem 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, catalystsystem 35.
Catalystsystem prepares the preparation of embodiment 36 catalystsystem 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, catalystsystem 36.
Catalystsystem prepares the preparation of embodiment 37 catalystsystem 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, catalystsystem 37.
Catalystsystem prepares the preparation of embodiment 38 catalystsystem 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, catalystsystem 38.
Catalystsystem prepares the preparation of embodiment 39 catalystsystem 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, catalystsystem 39.
Catalystsystem prepares the preparation of embodiment 40 catalystsystem 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, catalystsystem 40.
Catalystsystem prepares the preparation of embodiment 41 catalystsystem 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, catalystsystem 41.
Catalystsystem prepares the preparation of embodiment 42 catalystsystem 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, catalystsystem 42.
Catalystsystem prepares the preparation of embodiment 43 catalystsystem 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, catalystsystem 43.
Catalystsystem prepares the preparation of embodiment 44 catalystsystem 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, catalystsystem 44.
Catalystsystem prepares the preparation of embodiment 45 catalystsystem 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, catalystsystem 45.
Catalystsystem prepares the preparation of embodiment 46 catalystsystem 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, catalystsystem 46.
Catalystsystem prepares the preparation of embodiment 47 catalystsystem 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, catalystsystem 47.
Catalystsystem prepares the preparation of embodiment 48 catalystsystem 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, catalystsystem 48.
Catalystsystem prepares the preparation of embodiment 49 catalystsystem 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, catalystsystem 49.
Catalystsystem prepares the preparation of embodiment 50 catalystsystem 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, catalystsystem 50.
Catalystsystem prepares the preparation of embodiment 51 catalystsystem 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, catalystsystem 51.
Catalystsystem prepares the preparation of embodiment 52 catalystsystem 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, catalystsystem 52.
Catalystsystem prepares the preparation of embodiment 53 catalystsystem 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, catalystsystem 53.
Catalystsystem prepares the preparation of embodiment 54 catalystsystem 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, catalystsystem 54.
Catalystsystem prepares the preparation of embodiment 55 catalystsystem 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, catalystsystem 55.
Catalystsystem prepares the preparation of embodiment 56 catalystsystem 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, catalystsystem 56.
Catalystsystem prepares the preparation of embodiment 57 catalystsystem 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, catalystsystem 57.
Catalystsystem prepares the preparation of embodiment 58 catalystsystem 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, catalystsystem 58.
Catalystsystem prepares the preparation of embodiment 59 catalystsystem 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, catalystsystem 59.
Catalystsystem prepares the preparation of embodiment 60 catalystsystem 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, catalystsystem 60.
Aggregated application embodiment is following:
Application implementation example 1
Catalystsystem 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 PS white solid powder; Again this PS white solid powder is placed vacuum drying oven dry 48 hours, obtain exsiccant PS 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 PS n) be 6.6 ten thousand, MWD (M w/ M n) be 1.39.Normality between the nmr analysis PS (rrrr) is 100%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 271 ℃.
Application implementation example 2
Catalystsystem 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 PS white solid powder; Again this PS white solid powder is placed vacuum drying oven dry 48 hours, obtain exsiccant PS 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 PS n) be 36.3 ten thousand, MWD (M w/ M n) be 1.41.Normality between the nmr analysis PS (rrrr) is 100%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 272 ℃.
Application implementation example 3
Catalystsystem 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 PS white solid powder; Again this PS white solid powder is placed vacuum drying oven dry 48 hours, obtain exsiccant PS 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 PS n) be 53.6 ten thousand, MWD (M w/ M n) be 1.33.Normality between the nmr analysis PS (rrrr) is 100%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 272 ℃.
Application implementation example 4
Catalystsystem 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 PS white solid powder; Again this PS white solid powder is placed vacuum drying oven dry 48 hours, obtain exsiccant PS 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 PS n) be 86.3 ten thousand, MWD (M w/ M n) be 1.45.Normality between the nmr analysis PS (rrrr) is 100%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 270 ℃.
Application implementation example 5
Catalystsystem 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 PS white solid powder; Again this PS white solid powder is placed vacuum drying oven dry 48 hours, obtain exsiccant PS 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 PS n) be 1,000,000, MWD (M w/ M n) be 1.40.Normality between the nmr analysis PS (rrrr) is 100%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 272 ℃.
Application implementation example 6
Catalystsystem 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 PS white solid powder; Again this PS white solid powder is placed vacuum drying oven dry 48 hours, obtain exsiccant PS 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 PS n) be 13.7 ten thousand, MWD (M w/ M n) be 1.86.Normality between the nmr analysis PS (rrrr) is 80%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 266 ℃.
Application implementation example 7
Catalystsystem 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 PS white solid powder; Again this PS white solid powder is placed vacuum drying oven dry 48 hours, obtain exsiccant PS 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 PS n) be 20.6 ten thousand, MWD (M w/ M n) be 1.30.Normality between the nmr analysis PS (rrrr) is 100%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 270 ℃.
Application implementation example 8
Catalystsystem 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 PS white solid powder; Again this PS white solid powder is placed vacuum drying oven dry 48 hours, obtain exsiccant PS 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 PS n) be 40.5 ten thousand, MWD (M w/ M n) be 1.48.Normality between the nmr analysis PS (rrrr) is 100%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 271 ℃.
Application implementation example 9
Catalystsystem 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 PS white solid powder; Again this PS white solid powder is placed vacuum drying oven dry 48 hours, obtain exsiccant PS 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 PS n) be 55.7 ten thousand, MWD (M w/ M n) be 1.57.Normality between the nmr analysis PS (rrrr) is 100%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 270 ℃.
Application implementation example 10
Catalystsystem 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 PS white solid powder; Again this PS white solid powder is placed vacuum drying oven dry 48 hours, obtain exsiccant PS 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 PS n) be 18.5 ten thousand, MWD (M w/ M n) be 1.85.Normality between the nmr analysis PS (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 implementation example 11-23 is with application implementation 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
The application implementation example Catalystsystem St/Ln Polymerization temperature (℃) Polymerization time (min) Transformation efficiency (%) Polymerization activity (gmol Ln -1h -1) Normality between PS (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
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
23 23 2000 25 2 100 6.24×10 6 100％ 56.7 1.62 272
Application implementation example 24
Catalystsystem 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 PS white solid powder; Again this PS white solid powder is placed vacuum drying oven dry 48 hours, obtain exsiccant PS 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 PS n) be 760,000, MWD (M w/ M n) be 1.37.Normality between the nmr analysis PS (rrrr) is 100%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 271 ℃.
Application implementation example 25
Catalystsystem 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 PS white solid powder; Again this PS white solid powder is placed vacuum drying oven dry 48 hours, obtain exsiccant PS 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 PS n) be 42.4 ten thousand, MWD (M w/ M n) be 1.48.Normality between the nmr analysis PS (rrrr) is 100%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 270 ℃.
Application implementation example 26
Catalystsystem 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 PS white solid powder; Again this PS white solid powder is placed vacuum drying oven dry 48 hours, obtain exsiccant PS 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 PS n) be 57.6 ten thousand, MWD (M w/ M n) be 1.43.Normality between the nmr analysis PS (rrrr) is 100%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 272 ℃.
Application implementation example 27
Catalystsystem 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 PS white solid powder; Again this PS white solid powder is placed vacuum drying oven dry 48 hours, obtain exsiccant PS 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 PS n) be 80.7 ten thousand, MWD (M w/ M n) be 1.49.Normality between the nmr analysis PS (rrrr) is 100%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 271 ℃.
Application implementation example 28
Catalystsystem 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 PS white solid powder; Again this PS white solid powder is placed vacuum drying oven dry 48 hours, obtain exsiccant PS 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 PS n) be 98.7 ten thousand, MWD (M w/ M n) be 1.54.Normality between the nmr analysis PS (rrrr) is 100%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 272 ℃.
Application implementation example 29
Catalystsystem 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 PS white solid powder; Again this PS white solid powder is placed vacuum drying oven dry 48 hours, obtain exsiccant PS 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 PS n) be 23.7 ten thousand, MWD (M w/ M n) be 1.95.Normality between the nmr analysis PS (rrrr) is 89%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 267 ℃.
Application implementation example 30
Catalystsystem 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 PS white solid powder; Again this PS white solid powder is placed vacuum drying oven dry 48 hours, obtain exsiccant PS 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 PS n) be 31.2 ten thousand, MWD (M w/ M n) be 1.43.Normality between the nmr analysis PS (rrrr) is 100%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 270 ℃.
Application implementation example 31
Catalystsystem 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 PS white solid powder; Again this PS white solid powder is placed vacuum drying oven dry 48 hours, obtain exsiccant PS 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 PS n) be 48.5 ten thousand, MWD (M w/ M n) be 1.56.Normality between the nmr analysis PS (rrrr) is 100%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 272 ℃.
Application implementation example 32
Catalystsystem 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 PS white solid powder; Again this PS white solid powder is placed vacuum drying oven dry 48 hours, obtain exsiccant PS 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 PS n) be 58.7 ten thousand, MWD (M w/ M n) be 1.65.Normality between the nmr analysis PS (rrrr) is 100%.DSC measures the fusing point (T of syndiotactic polystyrene m) be 270 ℃.
Application implementation example 33
Catalystsystem 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 PS white solid powder; Again this PS white solid powder is placed vacuum drying oven dry 48 hours, obtain exsiccant PS 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 PS n) be 4.6 ten thousand, MWD (M w/ M n) be 1.90.Normality between the nmr analysis PS (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 implementation example 34-60 is with application implementation 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
The application implementation example Catalystsystem St/Ln Polymerization temperature (℃) Polymerization time (min) Transformation efficiency (%) Polymerization activity (g mol Ln -1h -1) Normality between PS (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
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
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 PS number-average molecular weight in 4.6～1,000,000 scopes, MWD narrower (1.30～1.98), fusing point is in 266～272 ℃ of scopes.Catalystsystem has higher adaptability to temperature, and in-20～80 ℃ polymerization temperature scope, the Gao Junke of normality between PS (rrrr) reaches 100%.

Claims (4)

1. the application of a constraint geometrical rear-earth title complex is characterized in that, the constraint geometrical rear-earth title complex is used for the catalystsystem of syndiotactic polymerization of phenylethylene; This catalystsystem 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
Described constraint geometrical rear-earth complex molecule formula is [R 1-(3-R 2-4-R 3-5-R 4-6-R 5) C 5N] LnX 2, structural formula is:
Figure FSB00000803264700011
Described R 1Be tetramethyl-ring pentadienyl or indenyl; Described R 2Be hydrogen or methyl; Described R 3Be hydrogen; Described R 4Be hydrogen; Described R 5Be hydrogen, methyl, phenyl, 2,6-3,5-dimethylphenyl or 2,4,6-triisopropyl phenyl; Described Ln is Sc, Y, Nd, Gd or Lu; Described X is CH 2SiMe 3Or 1,3-C 3H 5
2. the application of constraint geometrical rear-earth title complex as claimed in claim 1 is characterized in that, the described organic boron salt that is used for the catalystsystem of syndiotactic polymerization of phenylethylene is [Ph 3C] [B (C 6F 5) 4].
3. the application of constraint geometrical rear-earth title complex as claimed in claim 1 is characterized in that, the step and the condition of method for making of catalystsystem that the constraint geometrical rear-earth title complex is used for syndiotactic polymerization of phenylethylene is following: 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 the constraint geometrical rear-earth title complex selected for use, by proportioning at C 6～C 7Aromatic hydrocarbon solvent in mix, obtain the catalystsystem that homogeneous is used for syndiotactic polymerization of phenylethylene.
4. the application of constraint geometrical rear-earth title complex as claimed in claim 1 is characterized in that, the step and the condition of usage of catalystsystem that the constraint geometrical rear-earth title complex is used for syndiotactic polymerization of phenylethylene is following:
Get the toluene or the chlorobenzene solution that are used for the catalystsystem of syndiotactic polymerization of phenylethylene by described; Place the reactor drum 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 toluene or chlorobenzene solution and the described catalystsystem; Add styrene monomer; The mol ratio of the constraint geometrical rear-earth title complex in styrene monomer and the described catalystsystem is 250: 1～4000: 1, and polyreaction was carried out under-20～80 ℃ 1～30 minute, adds volumetric concentration and is 10% ethanol solution hydrochloride and stop polyreaction; Pour reaction soln in methyl alcohol sedimentation; Get PS white solid powder, place vacuum drying oven dry in this PS white solid powder again, obtain exsiccant PS white solid powder.
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