CN101880295A - Constrained Geometry Rare Earth Complexes and Their Preparation and Application of the Complexes in Syndiotactic Polymerization of Styrene - Google Patents

Abstract

由该限制几何构型稀上配合物与有机硼盐按mol比2∶1～1∶2组成的催化体系，在甲苯或氯苯溶剂中催化苯乙烯聚合制备间规聚苯乙烯。催化苯乙烯聚合时，在聚合温度-20～80℃范围内，单体转化率最高可达100％，活性最高可达1.25×10⁷g mol_Ln ^-1h^-1，所合成的聚苯乙烯间规度最高可达100％，熔点在266～272℃范围内，数均分子量在4.6～100万范围内，分子量分布最低可达1.30。The invention relates to a rare earth complex with constrained geometry configuration, a preparation method and the application of the complex in syndiotactic polymerization of styrene. The molecular formula of the rare earth complex with constrained geometry is [R ₁ -(3-R ₂ -4-R ₃ -5-R ₄ -6-R ₅ )C ₅ N]LnX ₂ , and the structural formula is:

Syndiotactic polystyrene is prepared by catalyzing the polymerization of styrene in toluene or chlorobenzene solvent by using the catalyst system composed of the rare complex of restricted geometric configuration and organic boron salt at a molar ratio of 2:1 to 1:2. When catalyzing the polymerization of styrene, the monomer conversion rate can reach up to 100% and the activity can reach up to 1.25×10 ⁷ g mol _Ln ^-1 h ^-1 at the polymerization temperature range of -20 to 80°C. The synthesized polystyrene The syndiotacticity can reach up to 100%, the melting point is in the range of 266-272°C, the number-average molecular weight is in the range of 4.6-1 million, and the molecular weight distribution can be as low as 1.30.

Description

Constrained Geometry Rare Earth Complexes and Their Preparation and Application of the Complexes in Syndiotactic Polymerization of Styrene

technical field

The present invention relates to a rare earth complex with constrained geometry configuration, a preparation method and the application of the complex in syndiotactic polymerization of styrene.

Background technique

The synthesis of polystyrene is mainly realized by free radical polymerization, anionic polymerization, cationic polymerization and Ziegler-Natta catalyst catalyzed polymerization. Polystyrene can be classified into atactic polystyrene, syndiotactic polystyrene, and isotactic polystyrene according to different three-dimensional configurations. Traditional free radical polymerization, anionic polymerization and cationic polymerization mainly obtain atactic polystyrene, Ziegler-Natta catalyst catalyzed styrene polymerization mainly obtains isotactic polystyrene, and high syndiotactic polystyrene was not produced by Japan Idemitsu Kosan until 1986 The company realizes it by using a metallocene catalyst of titanium to catalyze polymerization (N. Ishihara, T. Seimiya, M. Kuramoto and M. Uoi, Macromolecules, 1986, 19, 2464; EP210615A2 (1987); US5,252,693A1 (1993)). Syndiotactic polystyrene has become a very attractive material in industry due to its superior properties, such as high melting point, high crystallinity, high elastic modulus, low dielectric constant, low dissipation factor, and excellent heat and solvent resistance. force material. Since the Japanese Idemitsu Kosan Company first invented titanium metal complexes to catalyze high-syndiotactic polymerization of styrene in 1986, researchers have developed a series of titanium catalyst systems and applied for a series of patents, mainly because titanium metal complexes Catalyst systems, such as Cp*TiCl ₃ /MAO and Cp*TiR ₃ /B(C ₆ F ₅ ) ₃ , have very high catalytic activity in the polymerization of styrene and have very high syndiotacticity (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, DJGillis, MJTudoret, D.Jeremic, BKHunter and MCBaird, Organometallics, 1996, 15, 693; S.Ya.Knjazhanski, G.Cadenas, M.Garcia, CMPerez, IENifant′ev, IA Kashulin, PV Vchenko 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.). However, there are only few reports on the polymerization of styrene catalyzed by rare earth metal complexes. Some research groups have reported that rare earth metal complexes can obtain atactic polystyrene (Z.Shen, Polym.J., 1990,22,919; F.Yuan, Q.Shen and J .Sun, J.Organomet.Chem., 1997, 538, 241; AVKhvostov, VKBelsky, AISizov, BMBulychev and NBIvchenko, J.Organomet.Chem., 1997, 531, 19; S.Bogaert, JFCarpentier, T.Chenal, A . Mortreux and G. Ricart, Macromol. Chem. Phys., 2000, 201, 1813; K CHultzsch, P. Voth, K. Beckerle and TPSpaniol, Organometallics, 2000, 19, 228). The Yasuda research group reported that the alkyl compound of monolanthanocene polymerized styrene with lower activity to obtain rich syndiotactic polystyrene (K.Tanaka, M.Furo, E.Ihara and H.Yasuda, J.Polym.Sci. A: Polym. Chem., 2001, 39, 1382). In 2000, the Wakatsuki research group reported that samarium complexes can catalyze the polymerization of styrene with very high activity, but the obtained polystyrene is random (Z.Hou, Y.Zhang, H.Tezuka, P.Xie, O. Tardif, TA Koizumi. H. Yamazaki and Y. Wakatsuki, J. Am. Chem. Soc., 2000, 122, 10533). It was not until 2004 that rare earth metal complexes catalyzed the high syndiotactic polymerization of styrene made a real breakthrough. The Carpentier research group reported that the rare earth metal allyl compound [Cp-CMe ₂ -Flu]Ln(C ₃ H ₅ )(THF) can catalyze the high syndiotactic polymerization of styrene at a polymerization temperature of 60°C with one component, and the polymerization reaction There is very high activity, and the obtained polystyrene syndiotacticity (rrrr) can reach up to 100%, and the melting point is in the scope of 257～263 ℃ (E.Kirillov, CWLehmann, A.Razavi and JFCarpentier, J.Am.Chem. Soc., 2004, 126, 12240; EP1582536 A1; US2006/0116278 A1; US7,241,849B2). Almost at the same time, Hou's research group reported that the single rare earth metal alkyl compound (C ₅ Me ₄ SiMe ₃ )Ln(CH ₂ SiMe ₃ ) ₂ (THF) can catalyze the high Syndiotactic polymerization, the polymerization activity is as high as 1.36×10 ⁷ gmol _Ln ^-1 h ^-1 , the obtained polystyrene syndiotacticity (rrrr) can reach up to 100%, and the melting point is in the range of 268-273°C (Y.Luo, J . Baldamus and Z. Hou, J. Am. Chem. Soc., 2004, 126, 13910; US2007/0232758A1). Then some rare-earth metal complexes possessing alocene or heterocene ligands have also been reported to catalyze the high syndiotactic polymerization of styrene under the effect of cocatalysts (F.Jaroschik, T.Shima, X.Li, K.Mori, L.Ricard , XFLe Goff, F.Nief and Z.Hou, Organometallics, 2007, 26, 5654; AS Rodrigues, E.Kirillov, CW Lehmann, T.Roisnel, B.Vuillemin, A.Razavi and JF 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, CDC 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). However, there are no reports on the syndiotactic polymerization of styrene catalyzed by rare earth metal complexes with ligands of constrained geometry under the action of organoboron salt cocatalysts.

Contents of the invention

One of the objects of the present invention is to provide constrained geometry rare earth complexes.

The constrained geometry rare earth complex has a molecular formula of [R ₁ -(3-R ₂ -4-R ₃ -5-R ₄ -6-R ₅ )C ₅ N]LnX ₂ , and a structural formula of formula 1:

Formula 1

R ₁ in Formula 1 is a cyclopentadienyl derivative C ₅ A ₄ , an indenyl derivative C ₉ A ₆ or a fluorenyl derivative C ₁₃ A ₈ , and A is a substituent of a cyclopentadienyl, an indenyl The substituent or the substituent on the fluorenyl group, A is selected from hydrogen, aliphatic hydrocarbon group or aromatic hydrocarbon group; preferably hydrogen or methyl; R ₁ is preferably tetramethylcyclopentadienyl or indenyl; R ₂ is skeleton pyridine The substituent on the ring is selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl or phenyl, preferably hydrogen or methyl; _R3 is the substituent on the skeleton pyridine ring, selected from hydrogen, methyl , ethyl, isopropyl, tert-butyl or phenyl, preferably hydrogen; _R is a substituent on the skeleton pyridine ring, selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl or phenyl, Preferably hydrogen; _R is a substituent on the skeleton pyridine ring selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl, phenyl, 2,6-dimethylphenyl, 4-methylbenzene Trimethylphenyl, 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl or 2,6-di-tert-butylphenyl, preferably hydrogen, methyl, Phenyl, 2,6-dimethylphenyl or 2,4,6-triisopropylphenyl; Ln represents a rare earth metal selected from Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu , Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu, preferably Sc, Y, Nd, Gd or Lu; X is selected from CH ₂ SiMe ₃ , CH(SiMe ₃ ) ₂ , 1,3-C ₃ H _5. 1,3-C ₃ H ₄ (Me) or 1,3-C ₃ H ₃ (SiMe ₃ ) ₂ , preferably CH ₂ SiMe ₃ or 1,3-C ₃ H ₅ .

The preferred constrained geometry rare earth complex is any one of the following complexes of 1 to 28:

Complex 1: R ₁ =C ₅ Me ₄ , R ₂ =H, R ₃ =H, R ₄ =H, R ₅ =H, Ln=Sc, X=CH ₂ SiMe ₃ ;

Complex 2: R ₁ =C ₅ Me ₄ , R ₂ =H, R ₃ =H, R ₄ =H, R ₅ =H, Ln=Y, X=CH ₂ SiMe ₃ ;

Complex 3: R ₁ =C ₅ Me ₄ , R ₂ =H, R ₃ =H, R ₄ =H, R ₅ =H, Ln=Nd, X=CH ₂ SiMe ₃ ;

Complex 4: R ₁ =C ₅ Me ₄ , R ₂ =H, R ₃ =H, R ₄ =H, R ₅ =H, Ln=Gd, X=CH ₂ SiMe ₃ ;

Complex 5: R ₁ =C ₅ Me ₄ , R ₂ =H, R ₃ =H, R ₄ =H, R ₅ =H, Ln=Lu, X=CH ₂ SiMe ₃ ;

Complex 6: R ₁ =C ₅ Me ₄ , R ₂ =Me, R ₃ =H, R ₄ =H, R ₅ =H, Ln=Sc, X=CH ₂ SiMe ₃ ;

Complex 7: R ₁ =C ₅ Me ₄ , R ₂ =Me, R ₃ =H, R ₄ =H, R ₅ =H, Ln=Lu, X=CH ₂ SiMe ₃ ;

Complex 8: R ₁ =C ₅ Me ₄ , R ₂ =H, R ₃ =H, R ₄ =H, R ₅ =Me, Ln=Sc, X=CH ₂ SiMe ₃ ;

Complex 9: R ₁ =C ₅ Me ₄ , R ₂ =H, R ₃ =H, R ₄ =H, R ₅ =Me, Ln=Lu, X=CH ₂ SiMe ₃ ;

Complex 10: R ₁ =C ₅ Me ₄ , R ₂ =H, R ₃ =H, R ₄ =H, R ₅ =2,4,6-( ⁱ Pr) ₃ C ₆ H ₂ , Ln=Sc, X _{= CH2SiMe3} ;

Complex 11: R ₁ =C ₉ H ₆ , R ₂ =H, R ₃ =H, R ₄ =H, R ₅ =H, Ln=Sc, X=CH ₂ SiMe ₃ ;

Complex 12: R ₁ =C ₉ H ₆ , R ₂ =H, R ₃ =H, R ₄ =H, R ₅ =2,4,6-( ⁱ Pr) ₃ C ₆ H ₂ , Ln=Sc, X _{= CH2SiMe3} ;

Complex 13: R ₁ =C ₅ Me ₄ , R ₂ =H, R ₃ =H, R ₄ =H, R ₅ =H, Ln=Sc, X=1, 3-C ₃ H ₅ ;

Complex 14: R ₁ =C ₅ Me ₄ , R ₂ =H, R ₃ =H, R ₄ =H, R ₅ =H, Ln=Y, X=1, 3-C ₃ H ₅ ;

Complex 15: R ₁ =C ₅ Me ₄ , R ₂ =H, R ₃ =H, R ₄ =H, R ₅ =H, Ln=Nd, X=1, 3-C ₃ H ₅ ;

Complex 16: R ₁ =C ₅ Me ₄ , R ₂ =H, R ₃ =H, R ₄ =H, R ₅ =H, Ln=Gd, X=1, 3-C ₃ H ₅ ;

Complex 17: R ₁ =C ₅ Me ₄ , R ₂ =H, R ₃ =H, R ₄ =H, R ₅ =H, Ln=Lu, X=1, 3-C ₃ H ₅ ;

Complex 18: R ₁ =C ₅ Me ₄ , R ₂ =Me, R ₃ =H, R ₄ =H, R ₅ =H, Ln=Sc, X=1, 3-C ₃ H ₅ ;

Complex 19: R ₁ =C ₅ Me ₄ , R ₂ =Me, R ₃ =H, R ₄ =H, R ₅ =H, Ln=Lu, X=1, 3-C ₃ H ₅ ;

Complex 20: R ₁ =C ₅ Me ₄ , R ₂ =H, R ₃ =H, R ₄ =H, R ₅ =Me, Ln=Sc, X=1, 3-C ₃ H ₅ ;

Complex 21: R ₁ =C ₅ Me ₄ , R ₂ =H, R ₃ =H, R ₄ =H, R ₅ =Me, Ln=Lu, X=1, 3-C ₃ H ₅ ;

Complex 22: R ₁ =C ₅ Me ₄ , R ₂ =H, R ₃ =H, R ₄ =H, R ₅ =C ₆ H ₅ , Ln=Sc, X=1, 3-C ₃ H ₅ ;

Complex 23: R ₁ =C ₅ Me ₄ , R ₂ =H, R ₃ =H, R ₄ =H, R ₅ =2, 6-(Me) ₂ C ₆ H ₃ , Ln=Sc, X=1 , 3-C ₃ H ₅ ;

Complex 24: R ₁ =C ₅ Me ₄ , R ₂ =H, R ₃ =H, R ₄ =H, R ₅ =2,4,6-( ⁱ Pr) ₃ C ₆ H ₂ , Ln=Sc, X=1,3- _{C3H5 ;}

Complex 25: R ₁ =C ₉ H ₆ , R ₂ =H, R ₃ =H, R ₄ =H, R ₅ =H, Ln=Sc, X=1, 3-C ₃ H ₅ ;

Complex 26: R ₁ =C ₉ H ₆ , R ₂ =H, R ₃ =H, R ₄ =H, R ₅ =H, Ln=Lu, X=1, 3-C ₃ H ₅ ;

Complex 27: R ₁ =C ₉ H ₆ , R ₂ =H, R ₃ =H, R ₄ =H, R ₅ =2,4,6-( ⁱ Pr) ₃ C ₆ H ₂ , Ln=Sc, X=1,3- _{C3H5 ;}

Complex 28: R ₁ =C ₉ H ₆ , R ₂ =H, R ₃ =H, R ₄ =H, R ₅ =2,4,6-( ⁱ Pr) ₃ C ₆ H ₂ , Ln=Lu, X=1,3- _{C3H5 .}

The second object of the present invention is to provide a method for preparing rare earth complexes of constrained geometry, including: (1) a method for preparing rare earth alkyl complexes of constrained geometry; (2) a rare earth allyl complex of constrained geometry The method of making; respectively introduced as follows:

(1) The preparation method of rare earth alkyl complexes with restricted geometry configuration:

The synthetic route is as follows:

The conditions and steps are as follows: under the protection of N ₂ , the restricted geometry ligand R ₁ H-(3-R ₂ -4-R ₃ -5-R ₄ -6-R ₅ )C ₅ N was dissolved in THF and Put it at -78～0℃, add the n-hexane solution of 1.0～2.0mol/L n-butyllithium in the amount of 1 times the mol of the constrained geometry ligand, react for 1 hour, add the Rare earth trichloride in an amount 1 times the mol of the constrained geometry ligand, after reacting for 4 hours, add LiCH ₂ SiMe ₃ in an amount 2 times the mol of the constrained geometry ligand, and react at room temperature for 4 After 1 hour, the solvent was removed, extracted with hexane, and the hexane was concentrated to obtain a rare earth alkyl complex in a constrained geometry; the chemical formula of the rare earth trichloride was LnCl ₃ , wherein Ln was the same as Ln in Formula 1.

(2) The preparation method of rare earth allyl complexes with restricted geometry configuration:

The synthetic route is as follows:

The conditions and steps are as follows: under the protection of N ₂ , the restricted geometry ligand R ₁ H-(3-R ₂ -4-R ₃ -5-R ₄ -6-R ₅ )C ₅ N was dissolved in THF and Put it at -78～0°C, add the n-hexane solution whose concentration is 1.0～2.0mol/L n-butyllithium in an amount of 1 times the mol of the constrained geometry ligand, and react for 1 hour, then add the Rare earth trichloride in an amount 1 times the mol of the constrained geometry ligand, after reacting for 4 hours, add C ₃ H ₅ MgCl in an amount 2 times the mol of the constrained geometry ligand, and react at room temperature for 12 After 1 hour, remove the solvent, extract with toluene, and concentrate the toluene to obtain a rare earth allyl complex in a restricted geometry; the chemical formula of the rare earth chloride is LnCl ₃ , where Ln is the same as Ln in formula 1.

The above obtained constrained geometry configuration rare earth alkyl complexes and constrained geometry configuration rare earth allyl complexes were characterized by NMR, single crystal diffraction and elemental analysis. See the examples for details.

The third object of the present invention is to provide the application of the constrained geometry configuration rare earth complex in the syndiotactic polymerization of styrene.

The constrained geometry rare earth complex is used in a catalytic system for the syndiotactic polymerization of styrene; the catalytic system is composed of a constrained geometry rare earth complex and an organoboron salt in a molar ratio of 2:1 to 1:2 composition;

The organic boron salts are: [Ph ₃ C][B(C ₆ F ₅ ) ₄ ], [PhNMe ₂ H][BPh ₄ ], [PhNMe ₂ H][B(C ₆ F ₅ ) ₄ ] or B(C ₆ F ₅ ) ₃ , preferably [Ph ₃ C][B(C ₆ F ₅ ) ₄ ].

The steps and conditions of the preparation method of the catalytic system for the syndiotactic polymerization of styrene are as follows:

The rare earth complex with the molecular formula [R ₁ -(3-R ₂ -4-R ₃ -5-R ₄ -6-R ₅ )C ₅ N]LnX ₂ and the selected restricted geometry 0.5-2 times the mole amount of the type rare earth complex organic boron salt is uniformly mixed in a C ₆ -C ₇ aromatic hydrocarbon solvent according to the proportion to obtain a homogeneous catalyst system for syndiotactic polymerization of styrene.

The described catalytic system for the syndiotactic polymerization of styrene, the steps and conditions for the method for preparing syndiotactic polystyrene are as follows:

Get the toluene or chlorobenzene solution that is used for the catalytic system of styrene syndiotactic polymerization, be placed in the reactor through anhydrous, anaerobic treatment, the volume L of described solvent and described catalytic system The molar ratio of the rare earth complex of the restricted geometry configuration is 100:1 to 1000:1; adding styrene monomer, the molar ratio of the styrene monomer and the rare earth complex of the restricted geometry configuration in the catalytic system is 250 : 1 to 4000: 1, the polymerization reaction is carried out at -20 to 80°C for 1 to 30 minutes. Adding ethanol solution of hydrochloric acid with a volume concentration of 10% terminates the polymerization reaction, pours the reaction solution into methanol for sedimentation, and obtains a white solid powder of polystyrene, and then places the white solid powder of polystyrene in a vacuum drying oven to dry to obtain a dry polystyrene white solid powder.

The number-average molecular weight and molecular weight distribution of the above-mentioned syndiotactic polystyrene obtained are measured by high-temperature gel permeation chromatography (GPC), the melting point is measured by DSC, and the syndiotacticity (rrrr) of polystyrene is measured by proton nuclear magnetic resonance ( ¹ H NMR) and carbon spectrum ( ¹³ C NMR) spectrum calculations. See the examples for details.

Beneficial effects: the rare earth complex with constrained geometric configuration is simple to synthesize, and the yield is as high as 41% to 64%. The catalytic system composed of it and organoboron salt catalyzes the syndiotactic polymerization of styrene and has the characteristics of controllable polymerization. When catalyzing styrene polymerization, the monomer conversion rate can reach up to 100%, the activity can reach up to 1.25×10 ⁷ g mol _Ln ^-1 h ^-1 , and the synthesized polystyrene syndiotacticity (rrrr) can reach up to 100%. , the melting point is in the range of 266-272°C, the number-average molecular weight is in the range of 4.6-1 million, and the molecular weight distribution can reach as low as 1.30.

Detailed ways

Complex preparation examples are as follows:

Complex Preparation Example 1 Preparation of Complex 1

At -78°C, a n-hexane solution (1.2 mL, 1.2 mmol) of n-butyllithium with a concentration of 1.0 mol/L was added dropwise to 1-(2-pyridyl)-2,3,4,5- Tetramethylcyclopentadiene (0.24 g, 1.2 mmol) in THF (20 mL). After the reaction solution was reacted at this temperature for 1 hour, ScCl ₃ (0.18g, 1.2mmol) was added to the above reaction solution, and after 4 hours of reaction, LiCH ₂ SiMe ₃ (0.23g, 2.4mmol) was added, and the reaction was carried out at room temperature for 4 hours Finally, the solvent was removed in vacuo, the residue was extracted with hexane, and the hexane solution was concentrated to obtain 0.27 g of complex 1 as red crystals, with a yield of 54%. The molecular formula of the target substance in elemental analysis is C ₂₂ H ₃₈ NSi ₂ Sc (%): C, 62.84; H, 9.25; N, 3.28.

Preparation of complexes Example 2 Preparation of complexes 2-5

In the preparation method of the complex 2-5, except for the change of the reactant rare earth trichloride, other conditions and steps are the same as the complex preparation example 1, and the obtained restricted geometry rare earth alkyl complex 2-5 and the results are as follows Table 1:

Table 1 Constrained Geometry Rare Earth Alkyl Complexes 2-5

Complex Rare earth trichloride Target Molecular Formula Elemental analysis(%) Yield(%) 2 _YCl3 C ₂₂ H ₃₈ NSi ₂ Y C, 56.87; H, 8.36; N, 2.97 48 3 NdCl ₃ C ₂₂ H ₃₈ NSi ₂ Nd C, 49.81; H, 7.46; N, 2.61 45 4 _GdCl3 C ₂₂ H ₃₈ NSi ₂ Gd C, 49.52; H, 7.30; N, 2.56 63 5 _LuCl3 C ₂₂ H ₃₈ NSi ₂ Lu C, 47.86; H, 7.05; N, 2.48 61

Complex Preparation Example 3 Preparation of Complex 6

At -40°C, a n-hexane solution (0.8 mL, 1.2 mmol) of n-butyllithium with a concentration of 1.5 mol/L was added dropwise to 1-[2-(3-methyl)pyridyl]-2, 3,4,5-Tetramethylcyclopentadiene (0.26g, 1.2mmol) in tetrahydrofuran (20mL). After the reaction solution was reacted at this temperature for 1 hour, ScCl ₃ (0.18g, 1.2mmol) was added to the above reaction solution, and after 4 hours of reaction, LiCH ₂ SiMe ₃ (0.23g, 2.4mmol) was added, and the reaction was carried out at room temperature for 4 hours Finally, the solvent was removed in vacuo, the residue was extracted with hexane, and the hexane solution was concentrated to obtain 0.30 g of light red crystal complex 6 with a yield of 58%. The molecular formula of the target substance in elemental analysis is C ₂₃ H ₄₀ NSi ₂ Sc (%): C, 63.54; H, 9.42; N, 3.15.

Complex Preparation Example 4 Preparation of Complex 7

At -40°C, a n-hexane solution (0.8 mL, 1.2 mmol) of n-butyllithium with a concentration of 1.5 mol/L was added dropwise to 1-[2-(3-methyl)pyridyl]-2, 3,4,5-Tetramethylcyclopentadiene (0.26g, 1.2mmol) in tetrahydrofuran (20mL). After the reaction solution was reacted at this temperature for 1 hour, LuCl ₃ (0.34 g, 1.2 mmol) was added to the above reaction solution, and after 4 hours of reaction, LiCH ₂ SiMe ₃ (0.23 g, 2.4 mmol) was added, and the reaction was carried out at room temperature for 4 hours Finally, the solvent was removed in vacuo, the residue was extracted with hexane, and the hexane solution was concentrated to obtain 0.41 g of light red crystal complex 7 with a yield of 61%. The molecular formula of the target object in elemental analysis is C ₂₃ H ₄₀ NSi ₂ Lu (%): C, 48.93; H, 7.00; N, 2.38.

Complex Preparation Example 5 Preparation of Complex 8

At 40°C, a n-hexane solution (0.8 mL, 1.2 mmol) of n-butyllithium with a concentration of 1.5 mol/L was added dropwise to 1-[2-(6-methyl)pyridyl]-2,3 , in a solution of 4,5-tetramethylcyclopentadiene (0.26 g, 1.2 mmol) in tetrahydrofuran (20 mL). After the reaction solution was reacted at this temperature for 1 hour, ScCl ₃ (0.18g, 1.2mmol) was added to the above reaction solution, and after 4 hours of reaction, LiCH ₂ SiMe ₃ (0.23g, 2.4mmol) was added, and the reaction was carried out at room temperature for 4 hours Finally, the solvent was removed in vacuo, the residue was extracted with hexane, and the hexane solution was concentrated to obtain 0.25 g of light red crystal complex 8 with a yield of 48%. The molecular formula of the target substance in elemental analysis is C ₂₃ H ₄₀ NSi ₂ Sc (%): C, 63.48; H, 9.38; N, 3.19.

Complex Preparation Example 6 Preparation of Complex 9

At -40°C, a n-hexane solution (0.8 mL, 1.2 mmol) of n-butyllithium with a concentration of 1.5 mol/L was added dropwise to 1-[2-(6-methyl)pyridyl]-2, 3,4,5-Tetramethylcyclopentadiene (0.26g, 1.2mmol) in tetrahydrofuran (20mL). After the reaction solution was reacted at this temperature for 1 hour, LuCl ₃ (0.34 g, 1.2 mmol) was added to the above reaction solution, and after 4 hours of reaction, LiCH ₂ SiMe ₃ (0.23 g, 2.4 mmol) was added, and the reaction was carried out at room temperature for 4 hours Finally, the solvent was removed in vacuo, the residue was extracted with hexane, and the hexane solution was concentrated to obtain 0.31 g of light red crystal complex 9 with a yield of 46%. The molecular formula of the target object in elemental analysis is C ₂₃ H ₄₀ NSi ₂ Lu (%): C, 49.00; H, 6.97; N, 2.35.

Complex Preparation Example 7 Preparation of Complex 10

At -40°C, a n-hexane solution (0.8 mL, 1.2 mmol) of n-butyllithium with a concentration of 1.5 mol/L was added dropwise to 1-{2-[6-(2,4,6-triiso Propylphenyl)]pyridyl}-2,3,4,5-tetramethylcyclopentadiene (0.48g, 1.2mmol) in tetrahydrofuran (20mL). After the reaction solution was reacted at this temperature for 1 hour, ScCl ₃ (0.18g, 1.2mmol) was added to the above reaction solution, and after 4 hours of reaction, LiCH ₂ SiMe ₃ (0.23g, 2.4mmol) was added, and the reaction was carried out at room temperature for 4 hours Finally, the solvent was removed in vacuo, the residue was extracted with hexane, and the hexane solution was concentrated to obtain 0.32 g of light red crystal complex 10 with a yield of 42%. The molecular formula of the target object in elemental analysis is C ₃₇ H ₆₀ NSi ₂ Sc (%): C, 71.48; H, 9.65; N, 2.18.

Complex Preparation Example 8 Preparation of Complex 11

At -20°C, a n-hexane solution of n-butyllithium (0.6 mL, 1.2 mmol) with a concentration of 2.0 mol/L was added dropwise to 1-(2-pyridyl) indene (0.23 g, 1.2 mmol) solution in tetrahydrofuran (20 mL). After the reaction solution was reacted at this temperature for 1 hour, ScCl ₃ (0.18g, 1.2mmol) was added to the above reaction solution, and after 4 hours of reaction, LiCH ₂ SiMe ₃ (0.23g, 2.4mmol) was added, and the reaction was carried out at room temperature for 4 hours Finally, the solvent was removed in vacuo, the residue was extracted with hexane, and the hexane solution was concentrated to obtain 0.26 g of deep red crystal complex 11 with a yield of 53%. The molecular formula of the target substance in elemental analysis is C ₂₂ H ₃₂ NSi ₂ Sc (%): C, 63.98; H, 7.69; N, 3.31.

Complex Preparation Example 9 Preparation of Complex 12

At 0°C, a n-hexane solution (0.6 mL, 1.2 mmol) of n-butyllithium with a concentration of 2.0 mol/L was added dropwise to 1-{2-[6-(2,4,6-triisopropyl phenyl)]pyridyl}indene (0.48 g, 1.2 mmol) in tetrahydrofuran (20 mL). After the reaction solution was reacted at this temperature for 1 hour, ScCl ₃ (0.18g, 1.2mmol) was added to the above reaction solution, and after 4 hours of reaction, LiCH ₂ SiMe ₃ (0.23g, 2.4mmol) was added, and the reaction was carried out at room temperature for 4 hours Finally, the solvent was removed in vacuo, the residue was extracted with hexane, and the hexane solution was concentrated to obtain 0.52 g of deep red crystal complex 12 with a yield of 42%. The molecular formula of the target object in elemental analysis is C ₃₇ H ₅₄ NSi ₂ Sc (%): C, 72.18; H, 8.69; N, 2.17.

Complex Preparation Example 10 Preparation of Complex 13

At -78°C, a n-hexane solution (1.2 mL, 1.2 mmol) of n-butyllithium with a concentration of 1.0 mol/L was added dropwise to 1-(2-pyridyl)-2,3,4,5- Tetramethylcyclopentadiene (0.24 g, 1.2 mmol) in THF (20 mL). After the reaction solution was reacted at this temperature for 1 hour, ScCl ₃ (0.18g, 12mmol) was added to the above reaction solution. After 4 hours of reaction, C ₃ H ₅ MgCl (1.2mL, 2.4mmol, 2Min THF) was added, room temperature After reacting for 12 hours, the solvent was removed in vacuo, the residue was extracted with toluene, and the toluene solution was concentrated to obtain 0.25 g of red-yellow crystal complex 13 with a yield of 64%. The molecular formula of the elemental analysis target is C ₂₀ H ₂₆ NSc (%): C, 73.52; H, 7.90; N, 4.18.

Complex Preparation Example 11 Preparation of Complex 14

At -78°C, a n-hexane solution (1.2 mL, 1.2 mmol) of n-butyllithium with a concentration of 1.0 mol/L was added dropwise to 1-(2-pyridyl)-2,3,4,5- Tetramethylcyclopentadiene (0.24 g, 1.2 mmol) in THF (20 mL). After the reaction solution was reacted at this temperature for 1 hour, YCl ₃ (0.23g, 1.2mmol) was added to the above reaction solution. After 4 hours of reaction, C ₃ H ₅ MgCl (12mL, 2.4mmol, 2Min THF) was added, room temperature After reacting for 12 hours, the solvent was removed in vacuo, the residue was extracted with toluene, and the toluene solution was concentrated to obtain 0.26 g of red-yellow crystal complex 14 with a yield of 58%. The molecular formula of the target object in elemental analysis is C ₂₀ H ₂₆ NY (%): C, 64.80; H, 7.01; N, 3.68.

Complex Preparation Example 12 Preparation of Complex 15

At -40°C, a 1.0 mol/L n-butyl lithium n-hexane solution (1.2 mL, 1.2 mmol) was added dropwise to 1-(2-pyridyl)-2,3,4,5- Tetramethylcyclopentadiene (0.24 g, 1.2 mmol) in THF (20 mL). After the reaction solution was reacted at this temperature for 1 hour, NdCl ₃ (0.30 g, 1.2 mmol) was added to the above reaction solution, and after 4 hours of reaction, C ₃ H ₅ MgCl (1.2 mL, 2.4 mmol, 2Min THF) was added, After reacting at room temperature for 12 hours, the solvent was removed in vacuo, the residue was extracted with toluene, and the toluene solution was concentrated to obtain 0.28 g of red-yellow crystal complex 15 with a yield of 55%. The molecular formula of the target substance in elemental analysis is C ₂₀ H ₂₆ NNd (%): C, 56.37; H, 6.06; N, 3.21.

Complex Preparation Example 13 Preparation of Complex 16

At -20°C, a n-hexane solution (1.2 mL, 1.2 mmol) of n-butyllithium with a concentration of 1.0 mol/L was added dropwise to 1-(2-pyridyl)-2,3,4,5- Tetramethylcyclopentadiene (0.24 g, 1.2 mmol) in THF (20 mL). After the reaction solution was reacted at this temperature for 1 hour, GdCl ₃ (0.32 g, 1.2 mmol) was added to the above reaction solution, and after 4 hours of reaction, C ₃ H ₅ MgCl (1.2 mL, 2.4 mmol, 2Min THF) was added, After reacting at room temperature for 12 hours, the solvent was removed in vacuo, the residue was extracted with toluene, and the toluene solution was concentrated to obtain 0.32 g of red-yellow crystal complex 16 with a yield of 61%. The molecular formula of the target object in elemental analysis is C ₂₀ H ₂₆ NGd (%): C, 54.58; H, 5.89; N, 3.11.

Complex Preparation Example 14 Preparation of Complex 17

At 0°C, a n-hexane solution (1.2 mL, 1.2 mmol) of n-butyllithium with a concentration of 1.0 mol/L was added dropwise to 1-(2-pyridyl)-2,3,4,5-tetra A solution of methylcyclopentadiene (0.24 g, 1.2 mmol) in tetrahydrofuran (20 mL). After the reaction solution was reacted at this temperature for 1 hour, LuCl ₃ (0.34 g, 1.2 mmol) was added to the above reaction solution, and after 4 hours of reaction, C ₃ H ₅ MgCl (1.2 mL, 2.4 mmol, 2Min THF) was added, After reacting at room temperature for 12 hours, the solvent was removed in vacuo, the residue was extracted with toluene, and the toluene solution was concentrated to obtain 0.34 g of red-yellow crystal complex 17 with a yield of 63%. The molecular formula of the target object in elemental analysis is C ₂₀ H ₂₆ NLu (%): C, 52.42; H, 5.61; N, 2.99.

Complex Preparation Example 15 Preparation of Complex 18

At -40°C, a n-hexane solution (0.8 mL, 1.2 mmol) of n-butyllithium with a concentration of 1.5 mol/L was added dropwise to 1-[2-(3-methyl)pyridyl]-2, 3,4,5-Tetramethylcyclopentadiene (0.26g, 1.2mmol) in tetrahydrofuran (20mL). After the reaction solution was reacted at this temperature for 1 hour, ScCl ₃ (0.18 g, 1.2 mmol) was added to the above reaction solution, and after 4 hours of reaction, C ₃ H ₅ MgCl (1.2 mL, 2.4 mmol, 2Min THF) was added, After reacting at room temperature for 12 hours, the solvent was removed in vacuo, the residue was extracted with toluene, and the toluene solution was concentrated to obtain 0.22 g of red-yellow crystal complex 18 with a yield of 53%. The molecular formula of the target object in elemental analysis is C ₂₁ H ₂₈ NSc (%): C, 74.11; H, 8.21; N, 4.02.

Complex Preparation Example 16 Preparation of Complex 19

At -40°C, a n-hexane solution (0.8 mL, 1.2 mmol) of n-butyllithium with a concentration of 1.5 mol/L was added dropwise to 1-[2-(3-methyl)pyridyl]-2, 3,4,5-Tetramethylcyclopentadiene (0.26g, 1.2mmol) in tetrahydrofuran (20mL). After the reaction solution was reacted at this temperature for 1 hour, LuCl ₃ (0.34 g, 1.2 mmol) was added to the above reaction solution, and after 4 hours of reaction, C ₃ H ₅ MgCl (1.2 mL, 2.4 mmol, 2Min THF) was added, After reacting at room temperature for 12 hours, the solvent was removed in vacuo, the residue was extracted with toluene, and the toluene solution was concentrated to obtain 0.29 g of red-yellow crystal complex 19 with a yield of 51%. The molecular formula of the target object in elemental analysis is C ₂₁ H ₂₈ NLu (%): C, 53.53; H, 5.89; N, 2.88.

Complex Preparation Example 17 Preparation of Complex 20

At -40°C, a n-hexane solution (0.8 mL, 1.2 mmol) of n-butyllithium with a concentration of 1.5 mol/L was added dropwise to 1-[2-(6-methyl)pyridyl]-2, 3,4,5-Tetramethylcyclopentadiene (0.26g, 1.2mmol) in tetrahydrofuran (20mL). After the reaction solution was reacted at this temperature for 1 hour, ScCl ₃ (0.18 g, 1.2 mmol) was added to the above reaction solution, and after 4 hours of reaction, C ₃ H ₅ MgCl (1.2 mL, 2.4 mmol, 2Min THF) was added, After reacting at room temperature for 12 hours, the solvent was removed in vacuo, the residue was extracted with toluene, and the toluene solution was concentrated to obtain 0.20 g of red-yellow crystal complex 20 with a yield of 48%. The molecular formula of the target object in elemental analysis is C ₂₁ H ₂₈ NSc (%): C, 74.01; H, 8.25; N, 3.98.

Complex Preparation Example 18 Preparation of Complex 21

At -40°C, a n-hexane solution (0.8 mL, 1.2 mmol) of n-butyllithium with a concentration of 1.5 mol/L was added dropwise to 1-[2-(6-methyl)pyridyl]-2, 3,4,5-Tetramethylcyclopentadiene (0.26g, 1.2mmol) in tetrahydrofuran (20mL). After the reaction solution was reacted at this temperature for 1 hour, LuCl ₃ (0.34 g, 1.2 mmol) was added to the above reaction solution, and after 4 hours of reaction, C ₃ H ₅ MgCl (1.2 mL, 2.4 mmol, 2Min THF) was added, After reacting at room temperature for 12 hours, the solvent was removed in vacuo, the residue was extracted with toluene, and the toluene solution was concentrated to obtain 0.23 g of red-yellow crystal complex 21 with a yield of 41%. The molecular formula of the target object in elemental analysis is C ₂₁ H ₂₈ NLu (%): C, 53.45; H, 5.94; N, 2.85.

Complex Preparation Example 19 Preparation of Complex 22

At -40°C, a n-hexane solution (0.8 mL, 1.2 mmol) of n-butyllithium with a concentration of 15 mol/L was added dropwise to 1-[2-(6-phenyl)pyridyl]-2,3 , in a solution of 4,5-tetramethylcyclopentadiene (0.33 g, 1.2 mmol) in tetrahydrofuran (20 mL). After the reaction solution was reacted at this temperature for 1 hour, ScCl ₃ (0.18 g, 1.2 mmol) was added to the above reaction solution, and after 4 hours of reaction, C ₃ H ₅ MgCl (1.2 mL, 2.4 mmol, 2Min THF) was added, After reacting at room temperature for 12 hours, the solvent was removed in vacuo, the residue was extracted with toluene, and the toluene solution was concentrated to obtain 0.21 g of red-yellow crystal complex 22 with a yield of 44%. The molecular formula of the target object in elemental analysis is C ₂₆ H ₃₀ NSc (%): C, 77.48; H, 7.40; N, 3.38.

Complex Preparation Example 20 Preparation of Complex 23

At -40°C, a n-hexane solution (0.8 mL, 1.2 mmol) of n-butyllithium with a concentration of 1.5 mol/L was added dropwise to 1-{2-[6-(2,6-dimethylbenzene base)]pyridyl}-2,3,4,5-tetramethylcyclopentadiene (0.36 g, 1.2 mmol) in tetrahydrofuran (20 mL). After the reaction solution was reacted at this temperature for 1 hour, ScCl ₃ (0.18 g, 1.2 mmol) was added to the above reaction solution, and after 4 hours of reaction, C ₃ H ₅ MgCl (1.2 mL, 2.4 mmol, 2Min THF) was added, After reacting at room temperature for 12 hours, the solvent was removed in vacuo, the residue was extracted with toluene, and the toluene solution was concentrated to obtain 0.25 g of red-yellow crystal complex 23 with a yield of 48%. The molecular formula of the target object in elemental analysis is C ₂₈ H ₃₄ NSc (%): C, 78.00; H, 7.88; N, 3.16.

Complex Preparation Example 21 Preparation of Complex 24

At -40°C, a n-hexane solution (0.8 mL, 1.2 mmol) of n-butyllithium with a concentration of 1.5 mol/L was added dropwise to 1-{2-[6-(2,4,6-triiso Propylphenyl)]pyridyl}-2,3,4,5-tetramethylcyclopentadiene (0.48g, 1.2mmol) in tetrahydrofuran (20mL). After the reaction solution was reacted at this temperature for 1 hour, ScCl ₃ (0.18 g, 1.2 mmol) was added to the above reaction solution, and after 4 hours of reaction, C ₃ H ₅ MgCl (1.2 mL, 2.4 mmol, 2Min THF) was added, After reacting at room temperature for 12 hours, the solvent was removed in vacuo, the residue was extracted with toluene, and the toluene solution was concentrated to obtain 0.30 g of red-yellow crystal complex 24 with a yield of 48%. The molecular formula of the target object in elemental analysis is C ₃₅ H ₄₈ NSc (%): C, 79.48; H, 7.03; N, 2.54.

Complex Preparation Example 22 Preparation of Complex 25

At 0°C, add 2.0mol/L n-butyllithium in n-hexane (0.6mL, 1.2mmol) dropwise to 1-(2-pyridyl)indene (0.23g, 1.2mmol) in tetrahydrofuran (20 mL) solution. After the reaction solution was reacted at this temperature for 1 hour, ScCl ₃ (0.18 g, 1.2 mmol) was added to the above reaction solution, and after 4 hours of reaction, C ₃ H ₅ MgCl (1.2 mL, 2.4 mmol, 2Min THF) was added, After reacting at room temperature for 12 hours, the solvent was removed in vacuo, the residue was extracted with toluene, and the toluene solution was concentrated to obtain 0.16 g of yellow crystal complex 25 with a yield of 43%. The molecular formula of the elemental analysis target is C ₂₀ H ₂₀ NSc (%): C, 75.00; H, 6.21; N, 4.32.

Complex Preparation Example 23 Preparation of Complex 26

At 0°C, add 2.0mol/L n-butyllithium in n-hexane (0.6mL, 1.2mmol) dropwise to 1-(2-pyridyl)indene (0.23g, 1.2mmol) in tetrahydrofuran (20 mL) solution. After the reaction solution was reacted at this temperature for 1 hour, LuCl ₃ (0.34 g, 1.2 mmol) was added to the above reaction solution, and after 4 hours of reaction, C ₃ H ₅ MgCl (1.2 mL, 2.4 mmol, 2Min THF) was added, After reacting at room temperature for 12 hours, the solvent was removed in vacuo, the residue was extracted with toluene, and the toluene solution was concentrated to obtain 0.30 g of yellow crystal complex 26 with a yield of 56%. The molecular formula of the target object in elemental analysis is C ₂₀ H ₂₀ NLu (%): C, 53.34; H, 4.39; N, 3.04.

Complex Preparation Example 24 Preparation of Complex 27

At 0°C, a n-hexane solution (0.6 mL, 1.2 mmol) of n-butyllithium with a concentration of 2.0 mol/L was added dropwise to 1-{2-[6-(2,4,6-triisopropyl phenyl)]pyridyl}indene (0.48 g, 1.2 mmol) in tetrahydrofuran (20 mL). After the reaction solution was reacted at this temperature for 1 hour, ScCl ₃ (0.18 g, 1.2 mmol) was added to the above reaction solution, and after 4 hours of reaction, C ₃ H ₅ MgCl (1.2 mL, 2.4 mmol, 2Min THF) was added, After reacting at room temperature for 12 hours, the solvent was removed in vacuo, the residue was extracted with toluene, and the toluene solution was concentrated to obtain 0.29 g of yellow crystal complex 27 with a yield of 56%. The molecular formula of the target object in elemental analysis is C ₃₅ H ₄₂ NSc (%): C, 80.38; H, 8.01; N, 2.58.

Complex Preparation Example 25 Preparation of Complex 28

At 0°C, a n-hexane solution (0.6 mL, 1.2 mmol) of n-butyllithium with a concentration of 2.0 mol/L was added dropwise to 1-{2-[6-(2,4,6-triisopropyl phenyl)]pyridyl}indene (0.48 g, 1.2 mmol) in tetrahydrofuran (20 mL). After the reaction solution was reacted at this temperature for 1 hour, LuCl ₃ (0.34 g, 1.2 mmol) was added to the above reaction solution, and after 4 hours of reaction, C ₃ H ₅ MgCl (1.2 mL, 2.4 mmol, 2Min THF) was added, After reacting at room temperature for 12 hours, the solvent was removed in vacuo, the residue was extracted with toluene, and the toluene solution was concentrated to obtain 0.39 g of yellow crystal complex 28 with a yield of 50%. The molecular formula of the target object in elemental analysis is C ₃₅ H ₄₂ NLu (%): C, 64.45; H, 6.38; N, 2.07.

The preparation embodiment of catalytic system is as follows:

Preparation of Catalyst System Example 1 Catalyst System 1

At 25°C, add 10 μmol of complex 1, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 1 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic system 1.

Preparation of Catalyst System Example 2 Catalyst System 2

At 25°C, add 10 μmol of complex 1, 5 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 5 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic system 2.

Preparation of Catalyst System Example 3 Catalyst System 3

At 25°C, add 10 μmol of complex 1, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 5 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic system 3.

The preparation of catalytic system preparation embodiment 4 catalytic system 4

At 25°C, add 10 μmol of complex 1, 20 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 5 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic system4.

The preparation of catalytic system preparation embodiment 5 catalytic system 5

At 25°C, add 10 μmol of complex 1, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 10 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic system 5.

Preparation of Catalytic System Example 6 Preparation of Catalytic System 6

At 25°C, add 10 μmol of complex 1, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 10 ml of chlorobenzene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes. Catalytic system 6 was obtained.

Preparation of Catalyst System Example 7 Catalyst System 7

At -20°C, add 10 μmol of complex 1, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 2 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes. Catalytic system 7 was obtained.

Preparation of Catalyst System Example 8 Catalyst System 8

At 40°C, add 10 μmol of complex 1, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 2 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic system 8.

Preparation of Catalyst System Example 9 Preparation of Catalyst System 9

At 80°C, add 10 μmol of complex 1, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 5 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic system9.

Preparation of Catalyst System Example 10 Preparation of Catalyst System 10

At 25°C, add 10 μmol of complex 2, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 3 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic system 10.

Preparation of Catalyst System Example 11 Catalyst System 11

At 25°C, add 10 μmol of complex 3, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 5 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic system 11.

Preparation of Catalyst System Example 12 Catalyst System 12

At 25°C, add 10 μmol of complex 4, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 8 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic system 12.

Preparation of Catalyst System Example 13 Catalyst System 13

At 25°C, add 10 μmol of complex 5, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 1 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic system 13.

Preparation of Catalyst System Example 14 Catalyst System 14

At 25°C, add 10 μmol of complex 5, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 5 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic system 14.

Preparation of Catalyst System Example 15 Catalyst System 15

At 25°C, add 10 μmol of complex 5, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 10 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic system 15.

Preparation of Catalytic System Example 16 The preparation of catalytic system 16

At 25°C, add 10 μmol of complex 5, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 10 ml of chlorobenzene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes. Catalytic system 16 was obtained.

Preparation of Catalyst System Example 17 Catalyst System 17

At -20°C, add 10 μmol of complex 6, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 10 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes. Catalytic system 17 was obtained.

Preparation of Catalyst System Example 18 Catalyst System 18

At 80°C, add 10 μmol of complex 7, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 10 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic system 18.

Preparation of Catalyst System Example 19 Catalyst System 19

At 25°C, add 10 μmol of complex 8, 5 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 10 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic system19.

Preparation of Catalyst System Example 20 Preparation of Catalyst System 20

At 25°C, add 10 μmol of complex 9, 20 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 10 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic system 20.

Preparation of Catalytic System Example 21 Catalytic System 21

At 25°C, add 10 μmol of complex 10, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 10 ml of chlorobenzene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes. Catalytic system 21 was obtained.

Preparation of Catalyst System Example 22 Preparation of Catalyst System 22

At 25°C, add 10 μmol of complex 11, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 10 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic system22.

Preparation of Catalyst System Example 23 Catalyst System 23

At 25°C, add 10 μmol of complex 12, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 10 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic system23.

Preparation of Catalyst System Example 24 Catalyst System 24

At 25°C, add 10 μmol of complex 13, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 1 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic system24.

Preparation of Catalytic System Example 25 The preparation of catalytic system 25

At 25°C, add 10 μmol of complex 13, 5 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 5 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic system 25.

Preparation of Catalyst System Example 26 The preparation of Catalyst System 26

At 25°C, add 10 μmol of complex 13, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 5 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic system 26.

Preparation of Catalyst System Example 27 Catalyst System 27

At 25°C, add 10 μmol of complex 13, 20 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 5 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic systems27.

Preparation of Catalyst System Example 28 Catalyst System 28

At 25°C, add 10 μmol of complex 13, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 10 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic system 28.

Preparation of Catalyst System Example 29 Catalyst System 29

At 25°C, add 10 μmol of complex 13, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 10 ml of chlorobenzene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes. Catalytic system 29 was obtained.

Preparation of Catalyst System Example 30 Catalyst System 30

At -20°C, add 10 μmol of complex 13, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 2 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes. Catalytic system 30 was obtained.

Preparation of Catalyst System Example 31 Catalyst System 31

At 40°C, add 10 μmol of complex 13, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 2 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic system31.

Catalyst system preparation example 32 Preparation of catalytic system 32

At 80°C, add 10 μmol of complex 13, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 5 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic system32.

Catalyst System Preparation Example 33 Preparation of Catalyst System 33

At 25°C, add 10 μmol of complex 14, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 3 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic systems33.

Preparation of Catalyst System Example 34 Catalyst System 34

At 25°C, add 10 μmol of complex 15, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 5 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic systems34.

Preparation of Catalytic System Example 35 Preparation of Catalytic System 35

At 25°C, add 10 μmol of complex 16, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 8 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic systems35.

Preparation of Catalyst System Example 36 Preparation of Catalyst System 36

At 25°C, add 10 μmol of complex 17, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 1 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic systems36.

Preparation of Catalyst System Example 37 Catalyst System 37

At 25°C, add 10 μmol of complex 17, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 2 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic systems37.

Catalyst System Preparation Example 38 Preparation of Catalyst System 38

At 25°C, add 10 μmol of complex 17, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 4 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic systems38.

Preparation of Catalyst System Example 39 Catalyst System 39

At 25°C, add 10 μmol of complex 17, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 8 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic systems39.

Preparation of Catalytic System Example 40 The preparation of catalytic system 40

At 25°C, add 10 μmol of complex 17, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 10 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic system 40.

Preparation of Catalytic System Example 41 Catalytic System 41

At -20°C, add 10 μmol of complex 18, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 10 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes. Catalytic system 41 was obtained.

Preparation of Catalyst System Example 42 Catalyst System 42

At 80°C, add 10 μmol of complex 19, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 10 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic system42.

Preparation of Catalyst System Example 43 Catalyst System 43

At 25°C, add 10 μmol of complex 20, 5 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 5 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic systems43.

Preparation of Catalyst System Example 44 Catalyst System 44

At 25°C, add 10 μmol of complex 21, 20 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 5 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic systems44.

Preparation of Catalytic System Example 45 The preparation of catalytic system 45

At 25°C, add 10 μmol of complex 22, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 5 ml of chlorobenzene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes. Catalytic system 45 was obtained.

Preparation of Catalytic System Example 46 The preparation of catalytic system 46

At 25°C, add 10 μmol of complex 23, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 5 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic Systems 46.

Preparation of Catalytic System Example 47 The preparation of catalytic system 47

At 25°C, add 10 μmol of complex 24, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 5 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic Systems 47.

Preparation of Catalytic System Example 48 The preparation of catalytic system 48

At 25°C, add 10 μmol of complex 25, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 5 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic systems48.

Preparation of Catalyst System Example 49 Catalyst System 49

At 25°C, add 10 μmol of complex 25, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 10 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic systems49.

Preparation of Catalytic System Example 50 The preparation of catalytic system 50

At 25°C, add 10 μmol of complex 25, 5 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 5 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic system 50.

Preparation of Catalytic System Example 51 Catalytic System 51

At 25°C, add 10 μmol of complex 25, 20 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 5 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic System 51.

Preparation of Catalyst System Example 52 Catalyst System 52

At -20°C, add 10 μmol of complex 25, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 5 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes. Catalytic system 52 was obtained.

Preparation of Catalyst System Example 53 Catalyst System 53

At 60°C, add 10 μmol of complex 25, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 5 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic Systems 53.

Preparation of Catalyst System Example 54 Catalyst System 54

At 80°C, add 10 μmol of complex 25, 10 μmol [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 5 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic system54.

Preparation of Catalytic System Example 55 Catalytic System 55

At 25°C, add 10 μmol of complex 26, 5 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 5 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic Systems 55.

Preparation of Catalyst System Example 56 Catalyst System 56

At 25°C, add 10 μmol of complex 27, 20 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 5 ml of chlorobenzene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes. Catalytic system 56 was obtained.

Preparation of Catalytic System Example 57 The preparation of catalytic system 57

At 25°C, add 10 μmol of complex 28, 10 μmol of [Ph ₃ C]{B(C ₆ F ₅ ) ₄ ] and 5 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic Systems 57.

Preparation of Catalytic System Example 58 Catalytic System 58

At -20°C, add 10 μmol of complex 28, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 5 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes. Catalytic system 58 was obtained.

Preparation of Catalyst System Example 59 Catalyst System 59

At 80°C, add 10 μmol of complex 28, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 5 ml of toluene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes to obtain Catalytic Systems 59.

Preparation of Catalytic System Example 60 The preparation of catalytic system 60

At 25°C, add 10 μmol of complex 28, 10 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] and 5 ml of chlorobenzene solvent into a 25 ml anhydrous and anaerobic-treated polymerization bottle, and react for 2 minutes. Catalytic system 60 was obtained.

Examples of aggregation applications are as follows:

Application Example 1

Using the catalytic system 1 obtained in Preparation Example 1, add 2.5 mmol of styrene monomer (the molar ratio of monomer to complex 1 is 250:1). The polymerization bottle was placed in a constant temperature bath at 25°C, and reacted for 1 minute under stirring. Add 2ml of ethanol solution with a volume concentration of 10% hydrochloric acid to terminate the polymerization reaction, pour the reaction solution into 100ml of methanol for sedimentation, and obtain a polystyrene white solid powder, and then place the polystyrene white solid powder in a vacuum drying oven to dry for 48 Hour, obtain dry polystyrene white solid powder, net weight 0.26g. The conversion rate was 100%. The calculated polymerization activity is 1.56×10 ⁶ gmol _Sc ^-1 h ^-1 , the number average molecular weight (M _n ) of polystyrene analyzed by high temperature GPC is 66,000, and the molecular weight distribution (M _w /M _n ) is 1.39. The polystyrene syndiotacticity (rrrr) of nuclear magnetic analysis was 100%. The melting point (T _m ) of syndiotactic polystyrene determined by DSC was 271°C.

Application Example 2

Using the catalytic system 2 obtained in Preparation Example 2, add 10 mmol of styrene monomer (the molar ratio of monomer to complex 1 is 1000:1). The polymerization bottle was placed in a constant temperature bath at 25°C, and reacted for 1 minute under stirring. Add 2ml of ethanol solution with a volume concentration of 10% hydrochloric acid to terminate the polymerization reaction, pour the reaction solution into 100ml of methanol for sedimentation, and obtain a polystyrene white solid powder, and then place the polystyrene white solid powder in a vacuum drying oven to dry for 48 Hour, obtain dry polystyrene white solid powder, net weight 1.04g. The conversion rate was 100%. The calculated polymerization activity is 6.24×10 ⁶ g mol _Sc ^-1 h ^-1 , the number average molecular weight (M _n ) of polystyrene analyzed by high temperature GPC is 363,000, and the molecular weight distribution (M _w /M _n ) is 1.41. The polystyrene syndiotacticity (rrrr) of nuclear magnetic analysis was 100%. The melting point (T _m ) of syndiotactic polystyrene determined by DSC was 272°C.

Application Example 3

Using the catalytic system 3 obtained in Preparation Example 3, add 20 mmol of styrene monomer (the molar ratio of monomer to complex 1 is 2000:1). The polymerization bottle was placed in a constant temperature bath at 25°C, and reacted for 1.5 minutes under stirring. Add 2ml of ethanol solution with a volume concentration of 10% hydrochloric acid to terminate the polymerization reaction, pour the reaction solution into 100ml of methanol for sedimentation, and obtain a polystyrene white solid powder, and then place the polystyrene white solid powder in a vacuum drying oven to dry for 48 Hour, obtain dry polystyrene white solid powder, net weight 2.08g. The conversion rate was 100%. The calculated polymerization activity is 8.32×10 ⁶ gmol _Sc ^-1 h ^-1 , the number average molecular weight (M _n ) of polystyrene analyzed by high temperature GPC is 536,000, and the molecular weight distribution (M _w /M _n ) is 1.33. The polystyrene syndiotacticity (rrrr) of nuclear magnetic analysis was 100%. The melting point (T _m ) of syndiotactic polystyrene determined by DSC was 272°C.

Application Example 4

Using the catalytic system 4 obtained in Preparation Example 4, add 30 mmol of styrene monomer (the molar ratio of monomer to complex 1 is 3000:1). The polymerization bottle was placed in a constant temperature bath at 25°C, and reacted for 2 minutes under stirring. Add 2ml of ethanol solution with a volume concentration of 10% hydrochloric acid to terminate the polymerization reaction, pour the reaction solution into 100ml of methanol for sedimentation, and obtain a polystyrene white solid powder, and then place the polystyrene white solid powder in a vacuum drying oven to dry for 48 Hour, obtain dry polystyrene white solid powder, net weight 3.12g. The conversion rate was 100%. The calculated polymerization activity is 9.36×10 ⁶ g mol _Sc ^-1 h ^-1 , the number average molecular weight (M _n ) of polystyrene analyzed by high temperature GPC is 863,000, and the molecular weight distribution (M _w /M _n ) is 1.45. The polystyrene syndiotacticity (rrrr) of nuclear magnetic analysis was 100%. The melting point (T _m ) of syndiotactic polystyrene measured by DSC was 270°C.

Application Example 5

Using the catalytic system 5 obtained in Preparation Example 5, add 40 mmol of styrene monomer (the molar ratio of monomer to complex 1 is 4000:1). The polymerization bottle was placed in a constant temperature bath at 25°C, and reacted for 2 minutes under stirring. Add 2ml of ethanol solution with a volume concentration of 10% hydrochloric acid to terminate the polymerization reaction, pour the reaction solution into 100ml of methanol for sedimentation, and obtain a polystyrene white solid powder, and then place the polystyrene white solid powder in a vacuum drying oven to dry for 48 Hour, obtain dry polystyrene white solid powder, net weight 4.16g. The conversion rate was 100%. The calculated polymerization activity is 1.25×10 ⁷ g mol _Sc ^-1 h ^-1 , the number average molecular weight (M _n ) of polystyrene analyzed by high temperature GPC is 1 million, and the molecular weight distribution (M _w /M _n ) is 1.40. The polystyrene syndiotacticity (rrrr) of nuclear magnetic analysis was 100%. The melting point (T _m ) of syndiotactic polystyrene determined by DSC was 272°C.

Application Example 6

Using the catalytic system 6 obtained in Preparation Example 6, add 20 mmol of styrene monomer (the molar ratio of monomer to complex 1 is 2000:1). The polymerization bottle was placed in a constant temperature bath at 25°C, and reacted for 15 minutes under stirring. Add 2ml of ethanol solution with a volume concentration of 10% hydrochloric acid to terminate the polymerization reaction, pour the reaction solution into 100ml of methanol for sedimentation, and obtain a polystyrene white solid powder, and then place the polystyrene white solid powder in a vacuum drying oven to dry for 48 Hour, obtain dry polystyrene white solid powder, net weight 2.08g. The conversion rate was 100%. The calculated polymerization activity is 8.32×10 ⁶ gmol _Sc ^-1 h ^-1 , the number average molecular weight (M _n ) of polystyrene analyzed by high temperature GPC is 137,000, and the molecular weight distribution (M _w /M _n ) is 1.86. The polystyrene syndiotacticity (rrrr) of nuclear magnetic analysis was 80%. The melting point (T _m ) of syndiotactic polystyrene determined by DSC was 266°C.

Application Example 7

Using the catalytic system 7 obtained in Preparation Example 7, add 5 mmol of styrene monomer (the molar ratio of monomer to complex 1 is 500:1). The polymerization bottle was placed in a constant temperature bath at -20°C, and reacted for 5 minutes under stirring. Add 2ml of ethanol solution with a volume concentration of 10% hydrochloric acid to terminate the polymerization reaction, pour the reaction solution into 100ml of methanol for sedimentation, and obtain a polystyrene white solid powder, and then place the polystyrene white solid powder in a vacuum drying oven to dry for 48 Hour, obtain dry polystyrene white solid powder, net weight 0.52g. The conversion rate was 100%. The calculated polymerization activity is 6.24×10 ⁵ g mol _Sc ^-1 h ^-1 , the number average molecular weight (M _n ) of polystyrene analyzed by high temperature GPC is 206,000, and the molecular weight distribution (M _w /M _n ) is 1.30. The polystyrene syndiotacticity (rrrr) of nuclear magnetic analysis was 100%. The melting point (T _m ) of syndiotactic polystyrene determined by DSC was 270°C.

Application Example 8

Using the catalytic system 8 obtained in Preparation Example 8, add 10 mmol of styrene monomer (the molar ratio of monomer to complex 1 is 1000:1). The polymerization bottle was placed in a constant temperature bath at 40°C, and reacted for 1 minute under stirring. Add 2ml of ethanol solution with a volume concentration of 10% hydrochloric acid to terminate the polymerization reaction, pour the reaction solution into 100ml of methanol for sedimentation, and obtain a polystyrene white solid powder, and then place the polystyrene white solid powder in a vacuum drying oven to dry for 48 Hour, obtain dry polystyrene white solid powder, net weight 1.04g. The conversion rate was 100%. The calculated polymerization activity is 6.24×10 ⁶ g mol _Sc ^-1 h ^-1 , the number average molecular weight (M _n ) of polystyrene analyzed by high temperature GPC is 405,000, and the molecular weight distribution (M _w /M _n ) is 1.48. The polystyrene syndiotacticity (rrrr) of nuclear magnetic analysis was 100%. The melting point (T _m ) of syndiotactic polystyrene determined by DSC was 271°C.

Application Example 9

Using the catalytic system 9 obtained in Preparation Example 9, add 20 mmol of styrene monomer (the molar ratio of monomer to complex 1 is 2000:1). The polymerization bottle was placed in a constant temperature bath at 80°C, and reacted for 1 minute under stirring. Add 2ml of ethanol solution with a volume concentration of 10% hydrochloric acid to terminate the polymerization reaction, pour the reaction solution into 100ml of methanol for sedimentation, and obtain a polystyrene white solid powder, and then place the polystyrene white solid powder in a vacuum drying oven to dry for 48 Hour, obtain dry polystyrene white solid powder, net weight 2.08g. The conversion rate was 100%. The calculated polymerization activity is 1.25×10 ⁷ g mol _Sc ^-1 h ^-1 , the number average molecular weight (M _n ) of polystyrene analyzed by high temperature GPC is 557,000, and the molecular weight distribution (M _w /M _n ) is 1.57. The polystyrene syndiotacticity (rrrr) of nuclear magnetic analysis was 100%. The melting point (T _m ) of syndiotactic polystyrene determined by DSC was 270°C.

Application Example 10

Using the catalytic system 10 obtained in Preparation Example 10, add 10 mmol of styrene monomer (the molar ratio of monomer to complex 2 is 1000:1). The polymerization bottle was placed in a constant temperature bath at 25°C, and reacted for 30 minutes under stirring. Add 2ml of ethanol solution with a volume concentration of 10% hydrochloric acid to terminate the polymerization reaction, pour the reaction solution into 100ml of methanol for sedimentation, and obtain a polystyrene white solid powder, and then place the polystyrene white solid powder in a vacuum drying oven to dry for 48 Hour, obtain dry polystyrene white solid powder, net weight 0.83g. The conversion rate is 80%. The calculated polymerization activity is 1.67×10 ⁵ gmol _Y ^-1 h ^-1 , the number average molecular weight (M _n ) of polystyrene analyzed by high temperature GPC is 185,000, and the molecular weight distribution (M _w /M _n ) is 1.85. The polystyrene syndiotacticity (rrrr) of nuclear magnetic analysis was 93%. The melting point (T _m ) of syndiotactic polystyrene determined by DSC was 268°C.

The steps of the method for preparing syndiotactic polystyrene of Application Example 11-23 are the same as Application Example 1-10, and the conditions and the results obtained are as shown in Table 2:

Table 2 Application of rare earth alkyl complexes with constrained geometry in syndiotactic polymerization of styrene (St)

Application example Catalytic system St/Ln Polymerization temperature (℃) Polymerization time (min) Conversion rate(%) Polymerization activity (gmol _Ln ^-1 h ^-1 ) Syndiotacticity of polystyrene (rrrr) M _n ×10 ^-4 M _w /M _n T _m (°C) 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 Catalytic system St/Ln Polymerization temperature (℃) Polymerization time (min) Conversion rate(%) Polymerization activity (gmol _Ln ^-1 h ^-1 ) Syndiotacticity of polystyrene (rrrr) M _n ×10 ^-4 M _w /M _n T _m (°C) 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 twenty one twenty one 2000 25 20 100 6.24×10 ⁵ 84% 32.5 1.97 267 twenty two twenty two 2000 25 2 100 6.24×10 ⁶ 100% 62.3 1.46 271

Application example Catalytic system St/Ln Polymerization temperature (℃) Polymerization time (min) Conversion rate(%) Polymerization activity (gmol _Ln ^-1 h ^-1 ) Syndiotacticity of polystyrene (rrrr) M _n ×10 ^-4 M _w /M _n T _m (°C) twenty three twenty three 2000 25 2 100 6.24×10 ⁶ 100% 56.7 1.62 272

Application Example 24

Using the catalytic system 24 obtained in Preparation Example 24, add 2.5 mmol of styrene monomer (the molar ratio of monomer to complex 13 is 250:1). The polymerization bottle was placed in a constant temperature bath at 25°C, and reacted for 1 minute under stirring. Add 2ml of ethanol solution with a volume concentration of 10% hydrochloric acid to terminate the polymerization reaction, pour the reaction solution into 100ml of methanol for sedimentation, and obtain a polystyrene white solid powder, and then place the polystyrene white solid powder in a vacuum drying oven to dry for 48 Hour, obtain dry polystyrene white solid powder, net weight 0.26g. The conversion rate was 100%. The calculated polymerization activity is 1.56×10 ⁶ gmol _Sc ^-1 h ^-1 , the number average molecular weight (M _n ) of polystyrene analyzed by high temperature GPC is 760,000, and the molecular weight distribution (M _w /M _n ) is 1.37. The polystyrene syndiotacticity (rrrr) of nuclear magnetic analysis was 100%. The melting point (T _m ) of syndiotactic polystyrene determined by DSC was 271°C.

Application Example 25

Using the catalytic system 25 obtained in Preparation Example 25, add 10 mmol of styrene monomer (the molar ratio of monomer to complex 13 is 1000:1). The polymerization bottle was placed in a constant temperature bath at 25°C, and reacted for 1 minute under stirring. Add 2ml of ethanol solution with a volume concentration of 10% hydrochloric acid to terminate the polymerization reaction, pour the reaction solution into 100ml of methanol for sedimentation, and obtain a polystyrene white solid powder, and then place the polystyrene white solid powder in a vacuum drying oven to dry for 48 Hour, obtain dry polystyrene white solid powder, net weight 1.04g. The conversion rate was 100%. The calculated polymerization activity is 6.24×10 ⁶ gmol _Sc ^-1 h ^-1 , the number average molecular weight (M _n ) of polystyrene analyzed by high temperature GPC is 424,000, and the molecular weight distribution (M _w /M _n ) is 1.48. The polystyrene syndiotacticity (rrrr) of nuclear magnetic analysis was 100%. The melting point (T _m ) of syndiotactic polystyrene determined by DSC was 270°C.

Application Example 26

Using the catalytic system 26 obtained in Preparation Example 26, add 20 mmol of styrene monomer (the molar ratio of monomer to complex 13 is 2000:1). The polymerization bottle was placed in a constant temperature bath at 25°C, and reacted for 1.5 minutes under stirring. Add 2ml of ethanol solution with a volume concentration of 10% hydrochloric acid to terminate the polymerization reaction, pour the reaction solution into 100ml of methanol for sedimentation, and obtain a polystyrene white solid powder, and then place the polystyrene white solid powder in a vacuum drying oven to dry for 48 Hour, obtain dry polystyrene white solid powder, net weight 2.08g. The conversion rate was 100%. The calculated polymerization activity is 8.32×10 ⁶ gmol _Sc ^-1 h ^-1 , the number average molecular weight (M _n ) of polystyrene analyzed by high temperature GPC is 576,000, and the molecular weight distribution (M _w /M _n ) is 1.43. The polystyrene syndiotacticity (rrrr) of nuclear magnetic analysis was 100%. The melting point (T _m ) of syndiotactic polystyrene determined by DSC was 272°C.

Application Example 27

Using the catalytic system 27 obtained in Preparation Example 27, add 30 mmol of styrene monomer (the molar ratio of monomer to complex 13 is 3000:1). The polymerization bottle was placed in a constant temperature bath at 25°C, and reacted for 2 minutes under stirring. Add 2ml of ethanol solution with a volume concentration of 10% hydrochloric acid to terminate the polymerization reaction, pour the reaction solution into 100ml of methanol for sedimentation, and obtain a polystyrene white solid powder, and then place the polystyrene white solid powder in a vacuum drying oven to dry for 48 Hour, obtain dry polystyrene white solid powder, net weight 3.12g. The conversion rate was 100%. The calculated polymerization activity is 9.36×10 ⁶ gmol _Sc ^-1 h ^-1 , the number average molecular weight (M _n ) of polystyrene analyzed by high temperature GPC is 807,000, and the molecular weight distribution (M _w /M _n ) is 1.49. The polystyrene syndiotacticity (rrrr) of nuclear magnetic analysis was 100%. The melting point (T _m ) of syndiotactic polystyrene determined by DSC was 271°C.

Application Example 28

Using the catalytic system 28 obtained in Preparation Example 28, add 40 mmol of styrene monomer (the molar ratio of monomer to complex 13 is 4000:1). The polymerization bottle was placed in a constant temperature bath at 25°C, and reacted for 2 minutes under stirring. Add 2ml of ethanol solution with a volume concentration of 10% hydrochloric acid to terminate the polymerization reaction, pour the reaction solution into 100ml of methanol for sedimentation, and obtain a polystyrene white solid powder, and then place the polystyrene white solid powder in a vacuum drying oven to dry for 48 Hour, obtain dry polystyrene white solid powder, net weight 4.16g. The conversion rate was 100%. The calculated polymerization activity is 1.25×10 ⁷ gmol _Sc ^-1 h ^-1 , the number average molecular weight (M _n ) of polystyrene analyzed by high temperature GPC is 987,000, and the molecular weight distribution (M _w /M _n ) is 1.54. The polystyrene syndiotacticity (rrrr) of nuclear magnetic analysis was 100%. The melting point (T _m ) of syndiotactic polystyrene determined by DSC was 272°C.

Application Example 29

Using the catalytic system 29 obtained in Preparation Example 29, add 20 mmol of styrene monomer (the molar ratio of monomer to complex 13 is 2000:1). The polymerization bottle was placed in a constant temperature bath at 25°C, and reacted for 1.5 minutes under stirring. Add 2ml of ethanol solution with a volume concentration of 10% hydrochloric acid to terminate the polymerization reaction, pour the reaction solution into 100ml of methanol for sedimentation, and obtain a polystyrene white solid powder, and then place the polystyrene white solid powder in a vacuum drying oven to dry for 48 Hour, obtain dry polystyrene white solid powder, net weight 2.08g. The conversion rate was 100%. The calculated polymerization activity is 8.32×10 ⁶ gmol _Sc ^-1 h ^-1 , the number average molecular weight (M _n ) of polystyrene analyzed by high temperature GPC is 237,000, and the molecular weight distribution (M _w /M _n ) is 1.95. The polystyrene syndiotacticity (rrrr) of nuclear magnetic analysis was 89%. The melting point (T _m ) of syndiotactic polystyrene determined by DSC was 267°C.

Application Example 30

Using the catalytic system 30 obtained in Preparation Example 30, add 5 mmol of styrene monomer (the molar ratio of monomer to complex 13 is 500:1). The polymerization bottle was placed in a constant temperature bath at -20°C, and reacted for 5 minutes under stirring. Add 2ml of ethanol solution with a volume concentration of 10% hydrochloric acid to terminate the polymerization reaction, pour the reaction solution into 100ml of methanol for sedimentation, and obtain a polystyrene white solid powder, and then place the polystyrene white solid powder in a vacuum drying oven to dry for 48 Hour, obtain dry polystyrene white solid powder, net weight 0.52g. The conversion rate was 100%. The calculated polymerization activity is 6.24×10 ⁵ gmol _Sc ^-1 h ^-1 , the number average molecular weight (M _n ) of polystyrene analyzed by high temperature GPC is 312,000, and the molecular weight distribution (M _w /M _n ) is 1.43. The polystyrene syndiotacticity (rrrr) of nuclear magnetic analysis was 100%. The melting point (T _m ) of syndiotactic polystyrene determined by DSC was 270°C.

Application Example 31

Using the catalytic system 31 obtained in Preparation Example 31, add 10 mmol of styrene monomer (the molar ratio of monomer to complex 13 is 1000:1). The polymerization bottle was placed in a constant temperature bath at 40°C, and reacted for 1 minute under stirring. Add 2ml of ethanol solution with a volume concentration of 10% hydrochloric acid to terminate the polymerization reaction, pour the reaction solution into 100ml of methanol for sedimentation, and obtain a polystyrene white solid powder, and then place the polystyrene white solid powder in a vacuum drying oven to dry for 48 Hour, obtain dry polystyrene white solid powder, net weight 1.04g. The conversion rate was 100%. The calculated polymerization activity is 6.24×10 ⁶ gmol _Sc ^-1 h ^-1 , the number average molecular weight (M _n ) of polystyrene analyzed by high temperature GPC is 485,000, and the molecular weight distribution (M _w /M _n ) is 1.56. The polystyrene syndiotacticity (rrrr) of nuclear magnetic analysis was 100%. The melting point (T _m ) of syndiotactic polystyrene determined by DSC was 272°C.

Application Example 32

Using the catalytic system 32 obtained in Preparation Example 32, add 20 mmol of styrene monomer (the molar ratio of monomer to complex 13 is 2000:1). The polymerization bottle was placed in a constant temperature bath at 80°C, and reacted for 1 minute under stirring. Add 2ml of ethanol solution with a volume concentration of 10% hydrochloric acid to terminate the polymerization reaction, pour the reaction solution into 100ml of methanol for sedimentation, and obtain a polystyrene white solid powder, and then place the polystyrene white solid powder in a vacuum drying oven to dry for 48 Hour, obtain dry polystyrene white solid powder, net weight 2.08g. The conversion rate was 100%. The calculated polymerization activity is 1.25×10 ⁷ gmol _Sc ^-1 h ^-1 , the number average molecular weight (M _n ) of polystyrene analyzed by high temperature GPC is 587,000, and the molecular weight distribution (M _w /M _n ) is 1.65. The polystyrene syndiotacticity (rrrr) of nuclear magnetic analysis was 100%. The melting point (T _m ) of syndiotactic polystyrene determined by DSC was 270°C.

Application Example 33

Using the catalytic system 33 obtained in Preparation Example 33, add 5 mmol of styrene monomer (the molar ratio of monomer to complex 14 is 500:1). The polymerization bottle was placed in a constant temperature bath at 25°C, and reacted for 15 minutes under stirring. Add 2ml of ethanol solution with a volume concentration of 10% hydrochloric acid to terminate the polymerization reaction, pour the reaction solution into 100ml of methanol for sedimentation, and obtain a polystyrene white solid powder, and then place the polystyrene white solid powder in a vacuum drying oven to dry for 48 Hour, obtain dry polystyrene white solid powder, net weight 0.41g. The conversion rate is 80%. The calculated polymerization activity is 1.66×10 ⁵ g mol _Y ^-1 h ^-1 , the number average molecular weight (M _n ) of polystyrene analyzed by high temperature GPC is 46,000, and the molecular weight distribution (M _w /M _n ) is 1.90. The polystyrene syndiotacticity (rrrr) of nuclear magnetic analysis was 80%. The melting point (T _m ) of syndiotactic polystyrene determined by DSC was 266°C.

The steps of the method for preparing syndiotactic polystyrene of Application Example 34-60 are the same as Application Example 24-33, and the conditions and the results obtained are as shown in Table 3:

Table 3 Application of rare earth allyl complexes with constrained geometry in syndiotactic polymerization of styrene (St)

application example Catalytic system St/Ln Polymerization temperature (℃) Polymerization time (min) Conversion rate(%) Polymerization activity (g mol _Ln ^-1 h ^-1 ) Syndiotacticity of polystyrene (rrrr) M _n ×10 ^-4 M _w /M _n T _m (°C) twenty four twenty four 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 Catalytic system St/Ln Polymerization temperature (℃) Polymerization time (min) Conversion rate(%) Polymerization activity (g mol _Ln ^-1 h ^-1 ) Syndiotacticity of polystyrene (rrrr) M _n ×10 ^-4 M _w /M _n T _m (°C) 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 Catalytic system St/Ln Polymerization temperature (℃) Polymerization time (min) Conversion rate(%) Polymerization activity (g mol _Ln ^-1 h ^-1 ) Syndiotacticity of polystyrene (rrrr) M _n ×10 ^-4 M _w /M _n T _m (°C) 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

From the polymerization application examples 1-60, it can be concluded that all the rare earth complexes with constrained geometry can achieve high activity to styrene (1.66×10 ⁵ g mol _Ln ^-1 h ^-1 ~1.25×10 ⁷ g mol _Ln ^-1 h ^-1 ), highly syndiotactic (80%-100%) polymerization. The number-average molecular weight of the prepared polystyrene is in the range of 4.6-1 million, the molecular weight distribution is narrow (1.30-1.98), and the melting point is in the range of 266-272 DEG C. The catalytic system has high adaptability to temperature, and the polystyrene syndiotacticity (rrrr) can reach up to 100% within the polymerization temperature range of -20 to 80°C.

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:

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.