Magnesium rare earth complex and its preparation method and application

Abstract

The present invention relates to the field of organic synthesis technology, specifically providing a cyclopentadiene rare earth complex, a preparation method thereof, and applications thereof. The structure of the cyclopentadiene rare earth complex of the present invention is shown in Formula I. Compared with the prior art, the cyclopentadiene rare earth complex of the present invention comprises a ligand and a central metal, wherein the ligand is a cyclopentadiene containing an aromatic group, and the central metal is a rare earth element. The cyclopentadiene rare earth complex of the present invention is combined with an organoboron salt compound and an organoaluminum compound to form a catalytic system, which can catalyze the production of bimodal polystyrene.

Description

Technical Field

[0001] The present invention relates to the technical field of organic synthesis, and more particularly to a cyclopentadienyl rare earth complex and a preparation method and application thereof. Background Art

[0002] Syndiotactic polystyrene was synthesized and industrialized by Idemitsu Chemical in Japan in 1986. The product has a unimodal molecular weight distribution. Due to its high heat resistance, strong chemical resistance, high dimensional stability, low density, low dielectric properties, good hydrolytic stability, crystallinity, and a melting point of 270°C, it is currently used as a specialty polymer material, primarily in automotive electronic and electromagnetic components, machine casings, and high-end tableware. However, its high melting point results in poor processing properties.

[0003] Comparing with the development of polyethylene, we found that in order to achieve a balance between the rigidity, toughness and processing performance of polyethylene materials, academia and industry proposed the concept of polyethylene with a bimodal molecular weight distribution. The high molecular weight part gives the material high strength, high toughness and resistance to environmental stress cracking, while the low molecular weight part ensures the rigidity and lubrication of the material to improve processing performance.

[0004] Currently, achieving a bimodal distribution of polystyrene with high syndiotactic selectivity is crucial for its industrial applications, but few catalysts are available. Furthermore, conventional methods for producing syndiotactic polystyrene with a bimodal molecular weight distribution rely on two catalysts. Directly producing syndiotactic polystyrene with a bimodal molecular weight distribution using a single catalyst in a single reactor is rare. Summary of the Invention

[0005] In view of this, the object of the present invention is to provide a cyclopentadiene rare earth complex and its preparation method and application. The cyclopentadiene rare earth complex of the present invention is composed of a ligand and a central metal, the ligand is a cyclopentadiene containing an aromatic group, and the central metal is a rare earth element. The cyclopentadiene rare earth complex of the present invention is combined with an organic boron salt compound and an organic aluminum compound to obtain a catalytic system, which can catalyze the production of bimodal distribution polystyrene.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions:

[0007] A cyclopentadienyl rare earth complex as shown in formula I,

[0008]

[0009] In Formula I, L n For rare earth elements;

[0010] L w selected from Lewis bases;

[0011] L wThe number of is 0 to 3;

[0012] C p a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted fluorenyl group, or a substituted or unsubstituted fused heterocyclic cyclopentadienyl group;

[0013] X1 and X2 are independently selected from a group consisting of a silylmethyl-substituted alkyl group, a dimethylnitrogen-substituted benzyl group, and a substituted or unsubstituted allyl group;

[0014] Z is selected from C, Si or Ge;

[0015] R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 、R 11 、R 12 independently selected from hydrogen, halogen, C1-C10 alkyl, substituted or unsubstituted aryl;

[0016] q is an integer from 0 to 3.

[0017] The cyclopentadienyl rare earth complex of the present invention has the molecular formula [Cp-(R 11 ,R 12 )Z q -(2-R1-3-R2-4-R3-5-R4-6-R5)C5-(2-R6-3-R7-4-R8-5-R9-6-R 10 )C5-N]LnX1X2L w , where L n For rare earth elements; L w Selected from Lewis bases; C p is selected from substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted fused heterocyclic cyclopentadienyl; X1 and X2 are independently selected from one of silylmethyl substituted alkyl, dimethylnitrogen substituted benzyl, substituted or unsubstituted allyl; Z is selected from C, Si or Ge; R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 、R 11 、R 12 are independently selected from hydrogen, halogen, C1-C10 alkyl, substituted or unsubstituted aryl; q is an integer from 0 to 3.

[0018] In the present invention, X1 and X2 are independently selected from -CH2SiMe3, -CH(SiMe3)2, -CH2C6H4NMe2-o, -1,3-C3H5, -1,3-C3H4(Me) or -1,3-C3H3(SiMe3)2.

[0019] The cyclopentadiene rare earth complex provided by the invention consists of a ligand and a central metal. The ligand is a cyclopentadiene containing an aromatic group, and the central metal is a rare earth element.

[0020] In the present invention, L n One or more of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium;

[0021] The L w is a neutral Lewis base selected from tetrahydrofuran, diethyl ether, ethylene glycol dimethyl ether or pyridine;

[0022] R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 、R 11 、R 12 Independently selected from hydrogen, halogen, methyl, ethyl, isopropyl, tert-butyl or phenyl, 2,6-dimethylphenyl, 4-methylphenyl, mesitylene, 2,6-diisopropylphenyl or 2,4,6-triisopropylbenzene.

[0023] In the present invention, the cyclopentadienyl rare earth complex is any one of complexes 1 to 35:

[0024] Complex 1: Cp=C5Me4, Z=Si, R1=H, R2=H, R3=H, R4=H, R5=H, R6=H, R7=H, R8=H, R9=H, R 10 =H,R 11 =Me,R 12 =Me, Ln=Sc, X1=CH2SiMe3, X2=CH2SiMe3;

[0025] Complex 2: Cp=C5Me4, Z=Si, R1=H, R2=H, R3=H, R4=H, R5=H, R6=H, R7=H, R8=H, R9=H, R 10 =H,R 11 =Me,R 12 =Me, Ln=Y, X1=CH2SiMe3, X2=CH2SiMe3;

[0026] Complex 3: Cp=C5Me4, Z=Si, R1=H, R2=H, R3=H, R4=H, R5=H, R6=H, R7=H, R8=H, R9=H, R 10 =H,R 11 =Me,R 12 =Me, Ln=Lu, X1=CH2SiMe3, X2=CH2SiMe3;

[0027] Complex 4: Cp = C5Me4, Z = Si, R1 = H, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Dy, X1 = CH2SiMe3, X2 = CH2SiMe3;

[0028] Complex 5: Cp = C5Me4, Z = Si, R1 = H, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Er, X1 = CH2SiMe3, X2 = CH2SiMe3;

[0029] Complex 6: Cp = C5H4, Z = Si, R1 = H, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Sc, X1 = CH2SiMe3, X2 = CH2SiMe3;

[0030] Complex 7: Cp = C5H4, Z = Si, R1 = H, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Y, X1 = CH2SiMe3, X2 = CH2SiMe3;

[0031] Complex 8: Cp = C5H4, Z = Si, R1 = H, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Lu, X1 = CH2SiMe3, X2 = CH2SiMe3;

[0032] Complex 9: Cp = C 13 H 10 , Z = Si, R1 = H, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12=Me, Ln = Sc, X1 = CH2SiMe3, X2 = CH2SiMe3;

[0033] Complex 10: Cp = C 13 H 10 , Z = Si, R1 = H, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Y, X1 = CH2SiMe3, X2 = CH2SiMe3;

[0034] Complex 11: Cp = C 13 H 10 , Z = Si, R1 = H, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Lu, X1 = CH2SiMe3, X2 = CH2SiMe3;

[0035] Complex 12: Cp = C5Me4, Z = Si, R1 = Me, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R​​​​​​​​​​​​​​​​​​​​​​​​Complex 15: Cp = C5Me4, Z = Si, R1 = H, R2 = Me, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Sc, X1 = CH2SiMe3, X2 = CH2SiMe3;

[0039] Complex 16: Cp = C5Me4, Z = Si, R1 = H, R2 = Me, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Y, X1 = CH2SiMe3, X2 = CH2SiMe3;

[0040] Complex 17: Cp = C5Me4, Z = Si, R1 = H, R2 = Me, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Lu, X1 = CH2SiMe3, X2 = CH2SiMe3;

[0041] Complex 18: Cp = C5Me4, Z = Si, R1 = H, R2 = -OMe, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Sc, X1 = CH2SiMe3, X2 = CH2SiMe3;

[0042] Complex 19: Cp = C5Me4, Z = Si, R1 = H, R2 = -OMe, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Y, X1 = CH2SiMe3, X2 = CH2SiMe3;

[0043] Complex 20: Cp = C5Me4, Z = Si, R1 = H, R2 = -OMe, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12=Me, Ln = Lu, X1 = CH2SiMe3, X2 = CH2SiMe3;

[0044] Complex 21: Cp = C5Me4, Z = Si, R1 = H, R2 = H, R3 = CF3, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 =H, R 11 =Me, R 12 =Me, Ln = Sc, X1 = CH2SiMe3, X2 = CH2SiMe3;

[0045] Complex 22: Cp = C5Me4, Z = Si, R1 = H, R2 = H, R3 = CF3, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 =H, R 11 =Me, R 12 =Me, Ln = Y, X1 = CH2SiMe3, X2 = CH2SiMe3;

[0046] [[ID=二十一]]Complex 23: Cp = C5Me4, Z = Si, R1 = H, R2 = H, R3 = CF3, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R[[ID=二十二]] 10 [[ID=二十三]]=H, R[[ID=二十四]] 11 [[ID=二十五]]=Me, R[[ID=二十六]] 12 [[ID=二十七]]=Me, Ln = Lu, X1 = CH2SiMe3, X2 = CH2SiMe3;[[ID=二十八]] [[ID=二十九]]

[0047] [[ID=三十]]Complex 24: Cp = C5Me4, Z = Si, R1 = H, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R[[ID=三十一]] 10 [[ID=三十二]]=H, R[[ID=三十三]] 11 [[ID=三十四]]=Me, R[[ID=三十五]] 12 [[ID=三十六]]=Me, Ln = Sc, X1 = CH2C6H4NMe2 - o, X2 = CH2C6H4NMe2 - o;[[ID=三十七]] [[ID=三十八]]

[0048] [[ID=三十九]]Complex 25: Cp = C5Me4, Z = Si, R1 = H, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R[[ID=四十]] 10 [[ID=四十一]]=H, R[[ID=四十二]] 11 [[ID=四十三]]=Me, R[[ID=四十四]] 12 [[ID=四十五]]=Me, Ln = Y, X1 = CH2C6H4NMe2 - o, X2 = CH2C6H4NMe2 - o;[[ID=四十六]] [[ID=四十七]]

[0049] Complex 26: Cp = C5Me4, Z = Si, R1 = H, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Lu, X1 = CH2C6H4NMe2 - o, X2 = CH2C6H4NMe2 - o;

[0050] Complex 27: Cp = C5H4, Z = Si, R1 = H, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Sc, X1 = CH2C6H4NMe2 - o, X2 = CH2C6H4NMe2 - o;

[0051] Complex 28: Cp = C5H4, Z = Si, R1 = H, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Y, X1 = CH2C6H4NMe2 - o, X2 = CH2C6H4NMe2 - o;

[0052] Complex 29: Cp = C5H4, Z = Si, R1 = H, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Lu, X1 = CH2C6H4NMe2 - o, X2 = CH2C6H4NMe2 - o;

[0053] Complex 30: Cp = C 13 H 10 , Z = Si, R1 = H, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Sc, X1 = CH2C6H4NMe2 - o, X2 = CH2C6H4NMe2 - o;

[0054] Complex 31: Cp = C 13 H 10,Z=Si,R1=H,R2=H,R3=H,R4=H,R5=H,R6=H,R7=H,R8=H,R9=H,R 10 =H,R 11 =Me,R 12 =Me, Ln=Y, X1=CH2C6H4NMe2-o, X2=CH2C6H4NMe2-o;

[0055] Complex 32: Cp=C 13 H 10 ,Z=Si,R1=H,R2=H,R3=H,R4=H,R5=H,R6=H,R7=H,R8=H,R9=H,R 10 =H,R 11 =Me,R 12 =Me, Ln=Lu, X1=CH2C6H4NMe2-o, X2=CH2C6H4NMe2-o;

[0056] Complex 33: Cp=C5Me4, Z=Si, R1=H, R2=-OMe, R3=H, R4=H, R5=H, R6=H, R7=H, R8=H, R9=H, R 10 =H,R 11 =Me,R 12 =Me, Ln=Sc, X1=CH2C6H4NMe2-o, X2=CH2C6H4NMe2-o;

[0057] Complex 34: Cp=C5Me4, Z=Si, R1=H, R2=-OMe, R3=H, R4=H, R5=H, R6=H, R7=H, R8=H, R9=H, R 10 =H,R 11 =Me,R 12 =Me, Ln=Y, X1=CH2C6H4NMe2-o, X2=CH2C6H4NMe2-o;

[0058] Complex 35: Cp=C5Me4, Z=Si, R1=H, R2=-OMe, R3=H, R4=H, R5=H, R6=H, R7=H, R8=H, R9=H, R 10 =H,R 11 =Me,R 12 =Me, Ln=Lu, X1=CH2C6H4NMe2-o, X2=CH2C6H4NMe2-o.

[0059] In an embodiment of the present invention, the structure of the cyclopentadienyl rare earth complex is shown below:

[0060]

[0061] The present invention also provides a method for preparing the above-mentioned cyclopentadienyl rare earth complex, comprising: (1) reacting the compound represented by formula II with a lithiation reagent, L n Cl3 to obtain an intermediate product; (2) mixing the intermediate product with an alkylating agent to obtain a cyclopentadienyl rare earth complex;

[0062]

[0063] L n For rare earth elements;

[0064] In formula II, q is an integer from 0 to 3;

[0065] Z is selected from C, Si or Ge;

[0066] C p a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted fluorenyl group, or a substituted or unsubstituted fused heterocyclic cyclopentadienyl group;

[0067] R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 、R 11 、R 12 Independently selected from hydrogen, halogen, C1-C10 alkyl, and substituted or unsubstituted aryl.

[0068] In the present invention, the synthesis route of the cyclopentadienyl rare earth complex is as follows:

[0069]

[0070] In the present invention, the raw materials for preparing the intermediate product also include a Lewis base; the step (1) is specifically: firstly mixing the compound shown in formula II, the Lewis base and the lithiation reagent, and then n Cl3 mixed to obtain an intermediate product;

[0071] The molar ratio of the compound represented by formula II to the lithiation reagent is 1:(1-5), preferably 1:1;

[0072] The compound represented by formula II and L n The molar ratio of Cl3 is 1:(1-5), preferably 1:1;

[0073] The molar ratio of the intermediate product to the alkylating agent is 1:(2-10), preferably 1:2.

[0074] In the present invention, in step (1), the mixing time is 5 to 15 hours and the temperature is -78 to 0°C; in step (2), the mixing time is 1 to 10 hours and the temperature is -78 to 0°C.

[0075] The reaction of the present invention is preferably carried out in a nitrogen atmosphere; the alkylating agent is preferably LiCH2SiMe3 or LiCH2C6H4NMe2-o; and the lithiation agent is preferably n-butyllithium.

[0076] In one embodiment of the present invention, the method for preparing the cyclopentadienyl rare earth complex comprises:

[0077] Under nitrogen atmosphere, at -78℃~0℃, the compound (ligand) represented by formula II and Lewis base were mixed, and n-butyl lithium (concentration of 2.5M) in n-hexane in an amount of one times the molar number of the ligand was added, and the reaction was continued for 1 hour. Then, L-butyl lithium (concentration of 2.5M) in an amount of one times the molar number of the ligand was added. n Cl3, react for 4 hours, add an alkylating agent in an amount twice the molar number of the ligand and react for 4 hours, remove the solvent, extract with hexane, and concentrate to obtain a rare earth complex modified with an aromatic group.

[0078] The present invention also provides the use of the cyclopentadienyl rare earth complex in catalyzing styrene polymerization.

[0079] In the present invention, the styrene polymer has a bimodal distribution. The polystyrene has two molecular weights, one high and one low, and both have syndiotactic selectivities greater than 99%. The number average molecular weights of the styrene polymers range from 0.1 to 200,000 and 20,000 to 3,000,000, respectively. The molecular weight distributions of the two fractions are both between 1 and 3, and both molecular weights have syndiotactic structural units distributed throughout the polymer backbone.

[0080] In the present invention, the catalyst system for catalyzing the polymerization of styrene further comprises an organic boron salt compound and an organic aluminum compound.

[0081] In the present invention, the molar ratio of the organic boron salt compound to the cyclopentadienyl rare earth complex is 1:10 to 10:1, and the molar ratio of the organic aluminum compound to the cyclopentadienyl rare earth complex is (1 to 300):1.

[0082] In the present invention, the organic boron salt compound can be an ionic compound composed of an organic boron anion and a cation; the organic boron anion is selected from tetraphenylborate ([BPh4] - ), tetrakis(monofluorophenyl)borate, tetrakis(difluorophenyl)borate, tetrakis(trifluorophenyl)borate, tetrakis(tetrafluorophenyl)borate, tetrakis(pentafluorophenyl)borate ([B(C6F5)4] -), tetrakis(tetrafluoromethylphenyl)borate, tetrakis(tolyl)borate, tetrakis(xylyl)borate, (triphenyl, pentafluorophenyl)borate, [tris(pentafluorophenyl), phenyl]borate or undecyl-7,8-dicarbonundecaborate; the cation is selected from carbonium cations, oxonium cations, ammonium cations, phosphonium cations, cycloheptatrienyl cations or ferrocenium cations containing transition metals, and the carbonium cation includes a trisubstituted carbonium cation such as a triphenylcarbonium cation ([Ph3C] + ) and tri(substituted phenyl)carbonium cations, and more specific examples of the tri(substituted phenyl)carbonium cations include tri(tolyl)carbonium cations; ammonium cations include trialkylammonium cations such as trimethylammonium cations, triethylammonium cations ([NEt3H] + ), tripropylammonium cation and tributylammonium cation; N,N-dialkylanilinium cation such as N,N-dimethylanilinium cation ([PhNMe2H] + ), N,N-diethylanilinium cation and N,N-2,4,6-pentamethylanilinium cation and dialkylammonium cations such as diisopropylammonium cation and dicyclohexylammonium cation; phosphonium cations include triarylphosphonium cations such as triphenylphosphonium cation, tri(tolyl)phosphonium cation and tri(xylyl)phosphonium cation.

[0083] In one embodiment of the present invention, the organic boron salt compound is specifically selected from one or more of [Ph3C][B(C6F5)4], [PhNMe2H][BPh4], [NEt3H][BPh4], B(C6F5)3 and [PhNMe2H][B(C6F5)4];

[0084] The organoaluminum compound is selected from one or more of trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisopropylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum and ethyldi(p-tolyl)aluminum.

[0085] In the present invention, the preparation method of the catalyst system comprises: uniformly mixing a cyclopentadienyl rare earth complex, an organic boron salt and an organic aluminum compound in a hydrocarbon reagent according to a proportion to obtain a homogeneous catalyst system for bimodal syndiotactic polymerization of styrene.

[0086] In the present invention, the above catalyst system is used to catalyze the polymerization of styrene, and the polymerization process comprises the following steps:

[0087] mixing a hydrocarbon solvent, a styrene monomer, and a catalyst system to obtain polystyrene;

[0088] The hydrocarbon solvent is selected from one or more of aliphatic saturated hydrocarbons, aromatic hydrocarbons, aromatic halides and cycloalkanes;

[0089] The molar ratio of the hydrocarbon solvent to the rare earth complex in the catalyst system is 100:1 to 1000:1; the molar ratio of the styrene monomer to the rare earth complex in the catalyst system is 200:1 to 4000:1;

[0090] The polymerization temperature is -50 to 200° C., and the polymerization time is 5 minutes to 24 hours. The reaction is preferably carried out in a reactor treated in an anhydrous and oxygen-free environment.

[0091] In the present invention, the polymerization of styrene further comprises: adding an ethanol solution acidified with hydrochloric acid to terminate the polymerization reaction, pouring the reaction solution into ethanol for sedimentation, and drying the solid obtained by sedimentation to obtain a dry white solid powder of polystyrene.

[0092] The beneficial effects of the present invention are:

[0093] The cyclopentadiene rare earth complex of the present invention comprises a ligand and a central metal, wherein the ligand is a cyclopentadiene containing an aromatic group, and the central metal is a rare earth element. The cyclopentadiene rare earth complex of the present invention is combined with an organoboron salt compound and an organoaluminum compound to form a catalyst system. In a hydrocarbon solvent, controlled polymerization is performed to obtain polystyrene with a bimodal distribution. The method of the present invention produces the cyclopentadiene rare earth complex with a high yield of 50% to 60%.

[0094] The examples of the present invention demonstrate that when the cyclopentadienyl rare earth complex of the present invention is used to catalyze the polymerization of styrene, the monomer conversion rate can reach up to 100%, the syndiotacticity of the synthesized bimodal polystyrene can reach up to >99%, the melting point is within the range of 230-275°C, the number average molecular weight of the high molecular weight portion of the bimodal polystyrene is 20,000-3,000,000, and the number average molecular weight of the low molecular weight portion is 1,000-200,000, with a molecular weight distribution as low as 1.3. BRIEF DESCRIPTION OF THE DRAWINGS

[0095] Figure 1 is the H NMR spectrum of the styrene homopolymer in Example 36 of the present invention;

[0096] Figure 2 is the carbon NMR spectrum of the styrene homopolymer in Example 36 of the present invention;

[0097] Figure 3 is a DSC chart of the styrene homopolymer in Example 36 of the present invention;

[0098] Figure 4 This is the GPC chart of the styrene homopolymer in Example 36 of the present invention. DETAILED DESCRIPTION

[0099] The following will clearly and completely describe the technical solutions of the present invention in conjunction with the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0100] In order to further illustrate the present invention, the following examples are provided for detailed description. The raw materials used in the following examples of the present invention are all commercially available commodities.

[0101] 1. Preparation of Cyclopentadienyl Rare Earth Complexes

[0102] Example 1: Preparation of Complex 1

[0103]

[0104] At -78 ° C and nitrogen, a 2.5 M n-butyllithium n-hexane solution (0.3 mmol, 0.12 ml) was added dropwise to a solution of tetramethylcyclopentadienyl ligand (0.3 mmol, 0.1 g) in tetrahydrofuran (10 ml). After reacting for 1 h, ScCl3 (0.3 mmol, 0.1 g) was added to the reaction solution and reacted for 4 h. LiCH2SiMe3 (0.06 g, 0.6 mmol) was added and reacted for 4 h. The reaction solution was concentrated and recrystallized to obtain a light yellow cyclopentadienyl scandium complex 1, 0.10 g, with a yield of 50%. The target molecular formula of elemental analysis was C 35 H 58 NOScSi3 (%): C, 65.88; H, 9.16; N, 2.20; O, 2.51; Sc, 7.05; Si, 13.20.

[0105] Examples 2-5: Preparation of Complexes 2-5

[0106] In the preparation methods of complexes 2 to 5, except for the change of the reactant rare earth trichloride, other conditions and steps are the same as those in Example 1.

[0107] Complex 2, yield 55%, elemental analysis target molecular formula is C 35 H 58 NOSi3Y (%): C, 61.64; H, 8.57; N, 2.05; O, 2.35; Si, 12.35; Y, 13.04.

[0108] Complex 3, yield 54%, elemental analysis target molecular formula is C 35 H 58 NOSi3Lu (%): C, 54.73; H, 7.61; Lu, 22.78; N, 1.82; O, 2.08; Si, 10.97.

[0109] Complex 4, yield 52%, elemental analysis target molecular formula is C 35 H 58 NOSi3Dy (%): C, 55.64; H, 7.74; Dy, 21.51; N, 1.85; O, 2.12; Si, 11.15.

[0110] Complex 5, yield 56%, elemental analysis target molecular formula is C 35 H 58 NOSi3Er (%): C, 55.29; H, 7.69; Er, 22.00; N, 1.84; O, 2.10; Si, 11.08.

[0111] Example 6: Preparation of Complex 6

[0112]

[0113] At -78 ° C under nitrogen conditions, a 2.5 M n-butyllithium n-hexane solution (0.3 mmol, 0.12 ml) was added dropwise to a solution of cyclopentadienyl ligand (0.3 mmol, 0.08 g) in tetrahydrofuran (10 ml). After reacting for 1 h, ScCl3 (0.3 mmol, 0.1 g) was added to the above reaction solution and reacted for 4 h. LiCH2SiMe3 (0.06 g, 0.6 mmol) was added and reacted for 4 h. The reaction solution was concentrated and recrystallized to obtain a light yellow cyclopentadienyl scandium complex 6, 0.06 g, with a yield of 50%. The target molecular formula of elemental analysis was C 31 H 50 NOScSi3 (%): C, 63.98; H, 8.66; N, 2.41; O, 2.75; Sc, 7.72; Si, 14.48.

[0114] Examples 7-8: Preparation of Complexes 7-8

[0115] In the preparation method of complexes 7-8, except for the change of the reactant rare earth trichloride, other conditions and steps are the same as those in Example 6.

[0116] Complex 7, yield 55%, elemental analysis target molecular formula is C 31 H 50 NOYSi3 (%): C, 59.49; H, 8.05; N, 2.24; O, 2.56; Si, 13.46; Y, 14.20.

[0117] Complex 8, yield 54%, elemental analysis target molecular formula is C 31 H 50NOLuSi3 (%): C, 52.30; H, 7.08; Lu, 24.58; N, 1.97; O, 2.25; Si, 11.83.

[0118] Example 9: Preparation of Complex 9

[0119]

[0120] At -78 ° C under nitrogen conditions, a 2.5 M n-butyllithium n-hexane solution (0.3 mmol, 0.12 ml) was added dropwise to a solution of the fluorenyl ligand (0.3 mmol, 0.11 g) in tetrahydrofuran (10 ml). After reacting for 1 h, ScCl3 (0.3 mmol, 0.1 g) was added to the above reaction solution and reacted for 4 h. LiCH2SiMe3 (0.06 g, 0.6 mmol) was added and reacted for 4 h. The reaction solution was concentrated and recrystallized to obtain a light yellow cyclopentadienyl scandium complex 9, 0.1 g, with a yield of 50%. The target molecular formula of elemental analysis was C 39 H 54 NOScSi3 (%): C, 68.68; H, 7.98; N, 2.05; O, 2.35; Sc, 6.59; Si, 12.35.

[0121] Examples 10-11: Preparation of Complexes 10-11

[0122] In the preparation method of complexes 10-11, except for the change of the reactant rare earth trichloride, other conditions and steps are the same as those of Example 9.

[0123] Complex 10, yield 56%, elemental analysis target molecular formula is C 39 H 54 NOYSi3 (%): C, 64.52; H, 7.50; N, 1.93; O, 2.20; Si, 11.60; Y, 12.25.

[0124] The yield of complex 11 was 55%, and the target molecular formula of elemental analysis was C 39 H 54 NOLuSi3 (%): C, 57.68; H, 6.70; Lu, 21.55; N, 1.72; O, 1.97; Si, 10.38.

[0125] Example 12: Preparation of Complex 12

[0126]

[0127] At -78 ° C, a 2.5 M n-butyllithium n-hexane solution (0.3 mmol, 0.12 ml) was added dropwise to a solution of tetramethylcyclopentadienyl ligand (0.3 mmol, 0.11 g) in tetrahydrofuran (10 ml). After reacting for 1 h, ScCl3 (0.3 mmol, 0.1 g) was added to the reaction solution and reacted for 4 h. LiCH2SiMe3 (0.06 g, 0.6 mmol) was added and reacted for 4 h. The reaction solution was concentrated and recrystallized to obtain a light yellow cyclopentadienyl scandium complex 12, 0.11 g, with a yield of 50%. The target molecular formula of elemental analysis was C 36 H 60 NOScSi3 (%): C, 66.31; H, 9.27; N, 2.15; O, 2.45; Sc, 6.89; Si, 12.92.

[0128] Examples 13-14: Preparation of Complexes 13-14

[0129] In the preparation method of complexes 13-14, except for the change of the reactant rare earth trichloride, other conditions and steps are the same as those in Example 12.

[0130] Complex 13, yield 57%, elemental analysis target molecular formula is C 36 H 60 NOYSi3 (%): C, 62.12; H, 8.69; N, 2.01; O, 2.30; Si, 12.10; Y, 12.77.

[0131] Complex 14, yield 54%, elemental analysis target molecular formula is C 36 H 60 NOLuSi3 (%): C, 55.29; H, 7.73; Lu, 22.37; N, 1.79; O, 2.05; Si, 10.77.

[0132] Examples 15-17: Preparation of Complexes 15-17

[0133] In the preparation methods of complexes 15 to 17, except for the change of the substituent of reactant R2, other conditions and steps are the same as those of Examples 1 to 3.

[0134] Complex 15, yield 52%, elemental analysis target molecular formula is C 36 H 60 NOScSi3 (%): C, 62.12; H, 8.69; N, 2.01; O, 2.30; Si, 12.10; Y, 12.77.

[0135] Complex 16, yield 53%, elemental analysis target molecular formula is C 36 H 60NOYSi3 (%): C, 62.12; H, 8.69; N, 2.01; O, 2.30; Si, 12.10; Y, 12.77.

[0136] Complex 17, yield 55%, elemental analysis target molecular formula is C 36 H 60 NOLuSi3 (%): C, 55.29; H, 7.73; Lu, 22.37; N, 1.79; O, 2.05; Si, 10.77.

[0137] Examples 18-20: Preparation of Complexes 18-20

[0138] In the preparation methods of complexes 18 to 20, except for the change of the substituent of reactant R2, other conditions and steps are the same as those of Examples 1 to 3.

[0139] Complex 18, yield 51%, elemental analysis target molecular formula is C 36 H 60 NO2ScSi3 (%): C, 64.72; H, 9.05; N, 2.10; O, 4.79; Sc, 6.73; Si, 12.61.

[0140] Complex 19, yield 54%, elemental analysis target molecular formula is C 36 H 60 NO2YSi3 (%): C, 60.73; H, 8.49; N, 1.97; O, 4.49; Si, 11.83; Y, 12.49.

[0141] Complex 20, yield 55%, elemental analysis target molecular formula is C 36 H 60 NO2LuSi3 (%): C, 54.18; H, 7.58; Lu, 21.92; N, 1.76; O, 4.01; Si, 10.56.

[0142] Examples 21-23: Preparation of Complexes 21-23

[0143] In the preparation methods of complexes 21 to 23, except for the change of the substituent of reactant R3, other conditions and steps are the same as those of Examples 1 to 3.

[0144] Complex 21, yield 53%, elemental analysis target molecular formula is C 36 H 57 F3NOScSi3 (%): C, 61.24; H, 8.14; F, 8.07; N, 1.98; O, 2.27; Sc, 6.37; Si, 11.93.

[0145] Complex 22, yield 53%, elemental analysis target molecular formula is C 36 H 57 F3NOYSi3 (%): C, 57.65; H, 7.66; F, 7.60; N, 1.87; O, 2.13; Si, 11.23; Y, 11.85.

[0146] Complex 23, yield 51%, elemental analysis target molecular formula is C 36 H 57 F3NOLuSi3 (%): C, 51.72; H, 6.87; F, 6.82; Lu, 20.93; N, 1.68; O, 1.91; Si, 10.08.

[0147] Examples 24-26: Preparation of Complexes 24-26

[0148] In the preparation method of complexes 24-26, except for the change of lithium salt, other conditions and steps are the same as Examples 1-3.

[0149] Complex 24, yield 52%, elemental analysis target molecular formula is C 41 H 52 ScN3Si (%): C, 74.62; H, 7.94; N, 6.37; Sc, 6.81; Si, 4.26.

[0150] Complex 25, yield 51%, elemental analysis target molecular formula is C 41 H 52 YN3Si (%): C, 69.96; H, 7.45; N, 5.97; Si, 3.99; Y, 12.63.

[0151] Complex 26, yield 53%, elemental analysis target molecular formula is C 41 H 52 LuN3Si (%): C, 62.34; H, 6.64; Lu, 22.15; N, 5.32; Si, 3.56.

[0152] Examples 27-29: Preparation of Complexes 27-29

[0153] In the preparation methods of complexes 27-29, except for the change of lithium salt, other conditions and steps are the same as those in Examples 6-8.

[0154] Complex 27, yield 55%, elemental analysis target molecular formula is C 37 H 44 N3ScSi (%): C, 73.60; H, 7.35; N, 6.96; Sc, 7.45; Si, 4.65.

[0155] Complex 28, yield 53%, elemental analysis target molecular formula is C 37 H 44 N3YSi (%): C, 68.61; H, 6.85; N, 6.49; Si, 4.34; Y, 13.72.

[0156] Complex 29, yield 51%, elemental analysis target molecular formula is C 37 H 44 N3LuSi (%): C, 60.56; H, 6.04; Lu, 23.84; N, 5.73; Si, 3.83.

[0157] Examples 30-32: Preparation of Complexes 30-32

[0158] In the preparation method of complexes 30-32, except for the change of lithium salt, other conditions and steps are the same as Examples 9 to 11.

[0159] Complex 30, yield 50%, elemental analysis target molecular formula is C 45 H 48 ScN3Si (%): C, 76.78; H, 6.87; N, 5.97; Sc, 6.39; Si, 3.99.

[0160] Complex 31, yield 51%, elemental analysis target molecular formula is C 45 H 48 YN3Si (%): C, 72.27; H, 6.47; N, 5.62; Si, 3.76; Y, 11.89.

[0161] Complex 32, yield 50%, elemental analysis target molecular formula is C 45 H 48 LuN3Si (%): C, 64.81; H, 5.80; Lu, 20.98; N, 5.04; Si, 3.37.

[0162] Examples 33-35: Preparation of Complexes 33-35

[0163] In the preparation method of complexes 33-35, except for the change of lithium salt, other conditions and steps are the same as Examples 24-26.

[0164] Complex 33, yield 52%, elemental analysis target molecular formula is C 42 H 54 N3OSiSc (%): C, 73.12; H, 7.89; N, 6.09; O, 2.32; Sc, 6.52; Si, 4.07.

[0165] Complex 34, yield 53%, elemental analysis target molecular formula is C42 H 54 N3OSiY (%): C, 68.74; H, 7.42; N, 5.73; O, 2.18; Si, 3.83; Y, 12.11.

[0166] Complex 35, yield 51%, elemental analysis target molecular formula is C 42 H 54 N3OSiLu (%): C, 61.52; H, 6.64; Lu, 21.34; N, 5.12; O, 1.95; Si, 3.43.

[0167] 2. Preparation of bimodal polystyrene homopolymer

[0168] Example 36

[0169] In a glove box, 10 mL of toluene and 8 mmol of styrene monomer were added to a 10 mL vial and stirred; complex 1 (6.4 mg, 10 μmol), Al i Bu3 (0.2 ml, 100 μmol, 0.5 M toluene solvent) and triphenyl tetrakis(pentafluorophenyl)borate [Ph3C][B(C6F5)4] (9.2 mg, 10 μmol) were dissolved in toluene to prepare a catalyst composition; the catalyst composition was quickly injected into a penicillin bottle through a syringe to initiate polymerization. After the polymerization reaction took 24 hours, 2 ml of hydrochloric acid ethanol solution (v / v, 1:10) was added to terminate the polymerization reaction. The polymerization reaction liquid was then poured into 200 ml of ethanol for sedimentation, filtered, and vacuum dried for 24 hours to obtain a styrene polymer with a net weight of 0.83 g.

[0170] The product of this example is determined based on the homopolymer determined in C6D4Cl2 at 110°C. 1 HNMR and 13 CNMR spectrum was obtained; homopolymer glass transition temperature (T g ) and melting point (T m ) was determined by differential scanning calorimetry (DSC); the homopolymer number average molecular weight (M n ) and molecular weight distribution (M w / M n ) was determined by gel permeation chromatography (GPC) at 150°C using 1,2,4-trichlorobenzene as the mobile phase with polystyrene as the standard.

[0171] The styrene homopolymer obtained in Example 36 was analyzed by nuclear magnetic resonance and its 1 HNMR and 13 CNMR spectra, such as Figure 1 and Figure 2 As shown, Figure 1In the figure, the triplet quintet peaks at positions a and b indicate that the obtained polystyrene is syndiotactic polystyrene. Figure 2 The single peak at 145.5 ppm indicates that the syndiotactic selectivity of the obtained polystyrene is greater than 99%. The DSC graph is obtained by differential scanning calorimetry. Figure 3 shown. Figure 3 The DSC curve of the obtained polystyrene showed that Tg = 95.5 ° C and Tm = 271.1 ° C. The polystyrene was analyzed by size exclusion chromatography to obtain a GPC graph, as shown in FIG. Figure 4 shown. Figure 4 The GPC curve of the product is a bimodal distribution with a wide molecular weight distribution.

[0172] Example 37

[0173] In a glove box, 10 mL of toluene and 12 mmol of styrene monomer were added to a 10 mL vial and stirred. i Bu3 (0.2 ml, 100 μmol, 0.5 M toluene solvent) and triphenyl tetrakis(pentafluorophenyl)borate [Ph3C][B(C6F5)4] (9.2 mg, 10 μmol) were dissolved in toluene to prepare a catalyst composition; the catalyst composition was quickly injected into a penicillin bottle through a syringe to initiate polymerization. After the polymerization reaction lasted for 10 hours, 2 ml of hydrochloric acid ethanol solution (v / v, 1:10) was added to terminate the polymerization reaction. The polymerization reaction solution was then poured into 200 ml of ethanol for sedimentation, filtered, and vacuum dried for 24 hours to obtain a styrene polymer with a net weight of 1.23 g.

[0174] Example 38

[0175] In a glove box, 10 mL of toluene and 17 mmol of styrene monomer were added to a 10 mL vial and stirred. i Bu3 (0.2 ml, 100 μmol, 0.5 M toluene solvent) and triphenyl tetrakis(pentafluorophenyl)borate [Ph3C][B(C6F5)4] (9.2 mg, 10 μmol) were dissolved in toluene to prepare a catalyst composition; the catalyst composition was quickly injected into a penicillin bottle through a syringe to initiate polymerization. After the polymerization reaction lasted for 10 hours, 2 ml of hydrochloric acid ethanol solution (v / v, 1:10) was added to terminate the polymerization reaction. The polymerization reaction solution was then poured into 200 ml of ethanol for sedimentation, filtered, and vacuum dried for 24 hours to obtain a styrene polymer with a net weight of 1.75 g.

[0176] Table 1

[0177]

[0178] The above description of the disclosed embodiments will enable one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be readily apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention is not limited to the embodiments shown herein but is to be construed in the widest manner consistent with the principles and novel features disclosed herein.

Claims

1. A cyclopentadienyl rare earth complex as shown in formula I, （I）； In Formula I, L n One or more of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium; L w Selected from tetrahydrofuran, diethyl ether, ethylene glycol dimethyl ether or pyridine; L w The number of is 0~3; C p Selected from cyclopentadienyl, indenyl, fluorenyl; X1 and X2 are independently selected from -CH2SiMe3, -CH(SiMe3)2, -CH2C6H4NMe2-o, -1,3-C3H5, -1,3-C3H4(Me) or -1,3-C3H3(SiMe3)2; Z is selected from C, Si or Ge; R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 、R 11 、R 12 independently selected from hydrogen, halogen, methyl, ethyl, isopropyl, tert-butyl or phenyl, 2,6-dimethylphenyl, 4-methylphenyl, mesitylene, 2,6-diisopropylphenyl or 2,4,6-triisopropylbenzene; q is an integer from 0 to 3.

2. A cyclopentadienyl rare earth complex, characterized in that: It is any one of complexes 1 to 35: Complex 1: Cp = C5Me4, Z = Si, R1 = H, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Sc, X1 = CH2SiMe3, X2 = CH2SiMe3; Complex 2: Cp = C5Me4, Z = Si, R1 = H, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Y, X1 = CH2SiMe3, X2 = CH2SiMe3; Complex 3: Cp = C5Me4, Z = Si, R1 = H, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Lu, X1 = CH2SiMe3, X2 = CH2SiMe3; Complex 4: Cp = C5Me4, Z = Si, R1 = H, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Dy, X1 = CH2SiMe3, X2 = CH2SiMe3; Complex 5: Cp = C5Me4, Z = Si, R1= H, R2= H, R3= H, R4= H, R5= H, R6= H, R7= H, R8= H, R9= H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Er, X1 = CH2SiMe3, X2 =CH2SiMe3; Complex 6: Cp = C5H4, Z = Si, R1 = H, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Sc, X1 = CH2SiMe3, X2 = CH2SiMe3; Complex 7: Cp = C5H4, Z = Si, R1 = H, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Y, X1 = CH2SiMe3, X2 = CH2SiMe3; Complex 8: Cp = C5H4, Z = Si, R1 = H, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Lu, X1 = CH2SiMe3, X2 = CH2SiMe3; Complex 9: Cp = C 13 H 10 , Z = Si, R1 = H, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Sc, X1 = CH2SiMe3, X2 = CH2SiMe3; Complex 10: Cp = C 13 H 10 , Z = Si, R1 = H, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Y, X1 = CH2SiMe3, X2 = CH2SiMe3; Complex 11: Cp = C 13 H 10 , Z = Si, R1 = H, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Lu, X1 = CH2SiMe3, X2 = CH2SiMe3; Complex 12: Cp = C5Me4, Z = Si, R1 = Me, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Sc, X1 = CH2SiMe3, X2 = CH2SiMe3; Complex 13: Cp = C5Me4, Z = Si, R1 = Me, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Y, X1 = CH2SiMe3, X2 = CH2SiMe3; Complex 14: Cp = C5Me4, Z = Si, R1 = Me, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Lu, X1 = CH2SiMe3, X2 = CH2SiMe3; Complex 15: Cp = C5Me4, Z = Si, R1 = H, R2 = Me, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Sc, X1 = CH2SiMe3, X2 = CH2SiMe3; Complex 16: Cp = C5Me4, Z = Si, R1 = H, R2 = Me, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Y, X1 = CH2SiMe3, X2 = CH2SiMe3; Complex 17: Cp = C5Me4, Z = Si, R1 = H, R2 = Me, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Lu, X1 = CH2SiMe3, X2 = CH2SiMe3; Complex 18: Cp = C5Me4, Z = Si, R1 = H, R2 = OMe, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Sc, X1 = CH2SiMe3, X2 = CH2SiMe3; Complex 19: Cp = C5Me4, Z = Si, R1 = H, R2 = OMe, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Y, X1 = CH2SiMe3, X2 = CH2SiMe3; Complex 20: Cp = C5Me4, Z = Si, R1 = H, R2 = OMe, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Lu, X1 = CH2SiMe3, X2 = CH2SiMe3; Complex 21: Cp = C5Me4, Z = Si, R1 = H, R2 = H, R3 = CF3, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Sc, X1 = CH2SiMe3, X2 = CH2SiMe3; Complex 22: Cp = C5Me4, Z = Si, R1 = H, R2 = H, R3 = CF3, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Y, X1 = CH2SiMe3, X2 = CH2SiMe3; Complex 23: Cp = C5Me4, Z = Si, R1 = H, R2 = H, R3 = CF3, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Lu, X1 = CH2SiMe3, X2 = CH2SiMe3; Complex 24: Cp = C5Me4, Z = Si, R1 = H, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Sc, X1 = CH2C6H4NMe2-o, X2 = CH2C6H4NMe2-o; Complex 25: Cp = C5Me4, Z = Si, R1 = H, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Y, X1 = CH2C6H4NMe2-o, X2 = CH2C6H4NMe2-o; Complex 26: Cp = C5Me4, Z = Si, R1 = H, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Lu, X1 = CH2C6H4NMe2-o, X2 = CH2C6H4NMe2-o; Complex 27: Cp = C5H4, Z = Si, R1 = H, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Sc, X1 = CH2C6H4NMe2-o, X2 = CH2C6H4NMe2-o; Complex 28: Cp = C5H4, Z = Si, R1 = H, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Y, X1 = CH2C6H4NMe2-o, X2 = CH2C6H4NMe2-o; Complex 29: Cp = C5H4, Z = Si, R1 = H, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Lu, X1 = CH2C6H4NMe2-o, X2 = CH2C6H4NMe2-o; Complex 30: Cp = C 13 H 10 , Z = Si, R1 = H, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Sc, X1 = CH2C6H4NMe2 - o, X2 = CH2C6H4NMe2 - o; Complex 31: Cp = C 13 H 10 , Z = Si, R1 = H, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H,R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Y, X1 = CH2C6H4NMe2-o, X2 = CH2C6H4NMe2-o; Complex 32: Cp = C 13 H 10 , Z = Si, R1 = H, R2 = H, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Lu, X1 = CH2C6H4NMe2 - o, X2 = CH2C6H4NMe2 - o; Complex 33: Cp = C5Me4, Z = Si, R1 = H, R2 = OMe, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Sc, X1 = CH2C6H4NMe2-o, X2 = CH2C6H4NMe2-o; Complex 34: Cp = C5Me4, Z = Si, R1 = H, R2 = OMe, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Y, X1 = CH2C6H4NMe2-o, X2 = CH2C6H4NMe2-o; Complex 35: Cp = C5Me4, Z = Si, R1 = H, R2 = OMe, R3 = H, R4 = H, R5 = H, R6 = H, R7 = H, R8 = H, R9 = H, R 10 = H, R 11 = Me, R 12 = Me, Ln = Lu, X1 = CH2C6H4NMe2-o, X2 = CH2C6H4NMe2-o。 3. A cyclopentadienyl rare earth complex, characterized in that: Its structure is as follows: ； ； 。 4. The method for preparing the cyclopentadienyl rare earth complex according to claim 1, wherein: include: (1) The compound represented by formula II is reacted with a lithiation reagent, L n Cl3 mixed to obtain an intermediate product; (2) mixing the intermediate product and an alkylating agent to obtain a cyclopentadienyl rare earth complex; （Ⅱ） L n ,q,Z,C p , R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 、R 11 、R 12 As described in claim 1.

5. The method for preparing a cyclopentadienyl rare earth complex according to claim 4, wherein: The step (1) is specifically as follows: firstly, the compound represented by formula II is mixed with a lithiation reagent, and then n Cl3 mixed to obtain an intermediate product; The molar ratio of the compound represented by formula II to the lithiation reagent is 1:(1-5); The compound represented by formula II and L n The molar ratio of Cl3 is 1:(1~5); The molar ratio of the intermediate product to the alkylating agent is 1:(2~10).

6. The method for preparing a cyclopentadienyl rare earth complex according to claim 4, wherein: In step (1), the mixing time is 5 to 15 hours and the temperature is -78 to 0°C; In step (2), the mixing time is 1 to 10 hours and the temperature is -78 to 0°C.

7. Use of the cyclopentadienyl rare earth complex according to any one of claims 1 to 3 in catalyzing styrene polymerization.

8. The use according to claim 7, characterized in that Styrene polymers have a bimodal distribution.

9. The use according to claim 7, characterized in that The catalyst system for catalyzing the polymerization of styrene further comprises an organic boron salt compound and an organic aluminum compound.

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