CN106632767A - Rare-earth catalyst of nitrogen-containing heterocyclic carbene ligand and olefin polymerization catalyzing method of rare-earth catalyst - Google Patents

Rare-earth catalyst of nitrogen-containing heterocyclic carbene ligand and olefin polymerization catalyzing method of rare-earth catalyst Download PDF

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CN106632767A
CN106632767A CN201611201947.4A CN201611201947A CN106632767A CN 106632767 A CN106632767 A CN 106632767A CN 201611201947 A CN201611201947 A CN 201611201947A CN 106632767 A CN106632767 A CN 106632767A
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rare earth
earth catalyst
mec
rare
cabbeen
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CN106632767B (en
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李杨
谭睿
郭方
牛慧
史正海
李婷婷
杨珂
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Dalian University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/08—Butenes
    • C08F110/10—Isobutene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/08—Butenes
    • C08F210/10—Isobutene
    • C08F210/12—Isobutene with conjugated diolefins, e.g. butyl rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/01—High molecular weight, e.g. >800,000 Da.
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/03—Narrow molecular weight distribution, i.e. Mw/Mn < 3

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  • Chemical Kinetics & Catalysis (AREA)
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  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

The invention provides a rare-earth catalyst of a nitrogen-containing heterocyclic carbene ligand and an olefin polymerization catalyzing method of the rare-earth catalyst. The rare-earth catalyst comprises a part A and a part B, wherein the part A is nitrogen-containing heterocyclic carbene coordinated rare-earth complex LMR2X, L is a cyclopentadienyl ligand selected from a cyclopentadienyl ligand, an indenyl ligand and a fluorenyl ligand, X is the nitrogen-containing heterocyclic carbene ligand selected from imidazolyl carbene, imidazolinyl carbene, triazolyl carbene and thiazolyl carbene, M is rare-earth metal selected from Sc, Y, Lu, Gd, Sm and Nd, and R is alkyl directly connected with the rare-earth metal; the part B is organoboron reagents. By using the rare-earth catalyst of the nitrogen-containing heterocyclic carbene ligand, the chain transfer reaction of propylene monomers can be effectively inhibited so as to prepare the homopolymer and copolymer, with higher molecular weight and narrower molecular distribution, of the propylene monomers.

Description

The rare earth catalyst of one class nitrogen heterocyclic ring carbenes and its catalysis in olefine polymerization Method
Technical field
The invention belongs to high performance polymer material advanced manufacturing technology field, is related to a class and can be used for containing for olefinic polymerization The rare earth catalyst of nitrogen heterocycle carbine ligand.
Background technology
Chain transfer reaction is the restriction wide variety of bottleneck of rare earth catalyst, propylene monomer such as containing a methyl, Isobutylene monomer containing two methyl, due to more serious chain transfer reaction, it is difficult to which more high score is prepared using rare earth catalyst The polymer of son amount.Therefore, design synthesis can effectively suppress propylene, the rare earth catalyst of isobutylene type monomers chain transfer reaction The always challenging work in this area.Due to rare earth catalyst activity height, valence stability, olefinic monomer range of choice Extensively, molecular weight and its distribution can with Effective Regulation, therefore, effectively suppress chain transfer reaction, successfully synthesize HMW The high performance macromolecular material such as rare earth EP rubbers, rare earth butyl rubber, rare earth random polypropylene has become Polymer Synthesizing Holy grail.Chain transfer reaction of the rare earth catalyst reported at present to propylene, the class monomer of isobutene one in the course of the polymerization process suppresses Ability, causes that polymerization activity is low, is difficult to prepare the polymer of HMW.
The content of the invention
For prior art exist problem, the present invention provide a class nitrogen heterocyclic ring carbenes rare earth catalyst and its The method of catalysis in olefine polymerization, concrete technical scheme is as follows：
The rare earth catalyst of one class nitrogen heterocyclic ring carbenes includes A and B two parts, and A is the coordination of nitrogen heterocyclic ring Cabbeen Rare earth compounding LMR2X, wherein：L is cyclopentadienyl part, is selected generally from cyclopentadienyl ligands, indenyl ligands, fluorenyl ligand, dilute Native complex, cyclopentadienyl ligand structure formula are as follows, R1、R2、R3、R4And R5Selected from H, Me, Et, i-Pr, t-Bu, Ph, CH2Ph、 SiMe3、CH2SiMe3, R1、R2、R3、R4And R5It is identical or different；Cyclopentadienyl part cyclopentadienyl part preferably is selected from C5H5、 C5Me5、C5Me4SiMe3、C5HMe4、C5H2Me3、C5Me3(SiMe3)2、C5H3(SiMe3)2、C5Ph5；Indenyl ligands in cyclopentadienyl part It preferably is selected from 1-MeC9H6, 2-MeC9H6, 1- (CH3CH2)C9H6, 2- (CH3CH2)C9H6, 1- (t-Bu) C9H6, 1-Me3SiC9H6, 2- [3,5-(CF3)2C6H3]-C9H6, 2-C6H11-C9H6, 2- (3,5-Me2C6H3)-C9H6, 1-Me3Si-3-MeC9H5, 1-Me3Si-2- MeC9H5, 1-Me3Si-2-PhC9H5, 1-Me3Si-3-(CH3CH2)C9H5, 1-Me3Si-3-(t-Bu)C9H5, 1,3- (Me3Si)2C9H5, 1-Me3Si-3,4,7-Me3C9H4, 1-Me3Si-2-Me-4-PhC9H4, 1,3- (Me3Si)2-2-MeC9H4, 2-Me-4,7- Me2C9H4, 2-Me-4,6-Me2C9H4, 3-Me3Si-4,6-Me2C9H4, 1-Me3Si-2-Me-4,6-(i-Pr)2C9H3, 1-Me3Si- 2-Me-4,7-Me2C9H3；Fluorenyl ligand preferably is selected from 2-MeC in cyclopentadienyl part13H8, 9-MeC13H8, 9- (CH3CH2)C13H8, 9- (i- Pr)C13H8, 9- (t-Bu) C13H8, 9-C6H11C13H8, 9-PhC13H8, 9- (2-MeC6H4)C13H8, 9- (2,4,6-Me3C6H2) C13H8, 9-Me3SiC13H8, 2,7- (t-Bu)2-C13H7, 2,7- (t-Bu)2-9-Me3SiC13H6；M is rare earth metal, selected from Sc, Y, Lu, Gd, Sm, Nd, preferably are selected from Sc, Y, Lu；R is the alkyl being joined directly together with rare earth metal, selected from CH2SiMe3、 CH2C6H4NMe2-o、CH2Ph、CH2CH=CH2、1,3-C3H4(Me)、1,3-C3H3(SiMe3)2、CH(SiMe3)2、Me、Et、i- Pr、t-Bu；X is nitrogen heterocycle carbine ligand, selected from imidazole radicals Cabbeen, imidazolinyl Cabbeen, triazolyl Cabbeen, thiazolyl Cabbeen, Preferably be selected from 1,3- dimethyl-imidazolyl Cabbeens, 1,3- diisopropyl-imidazolium base Cabbeens, 1,3- dimethyl-imidazolidin base Cabbeens, 1,3- diisopropyl-imidazolium quinoline base Cabbeens, 1,3- dimethyl-triazolyl Cabbeen, 1,3- diisopropyls-triazolyl Cabbeen, 1- first Base-thiazolyl Cabbeen, 1- isopropyls-thiazolyl Cabbeen；B is organoboron reagent, selected from [Ph3C][B(C6F5)4]、[PhMe2NH] [B(C6F5)4]、B(C6F5)3In the mixture of one or more；Me is methyl, Et is ethyl, Pr is propyl group, Bu is butyl, Ph is phenyl.
Rare earth compounding/cyclopentadienyl ligand structure formula
Using the rare earth catalyst of above-mentioned nitrogen heterocyclic ring carbenes, can be used for catalysis in olefine polymerization and prepare polyolefin, gather The number-average molecular weight of alkene is 10 × 104-180×104, preferably 30 × 104-150×104；Alkene is selected from ɑ-alkene and its spreads out The mixture of one or more in biological, conjugated alkene and its derivative, cyclenes hydrocarbons and their derivates；Alkene preferably is selected from second Alkene, propylene, n-butene, isobutene, butadiene, isoprene, laurene, styrene, ENB, dicyclopentadiene, oneself two The mixture of one or more in alkene；Alkene derivatives are selected generally from the alkene containing nitrogen, oxygen, chlorine, bromine atoms functional group and spread out Biology, preferably is selected from containing nitrogen, oxygen, chlorine, the ethene derivatives of bromine atoms functional group, butadiene derivatives, styrene derivative, drop The mixture of one or more in borneol ene derivative；Polymerization is selected from polymerisation in solution, polymerisation in bulk；Needed for polymerisation in solution Organic solvent be selected from pentane, hexane, heptane, hexamethylene, benzene,toluene,xylene, chlorobenzene, dichloro-benzenes, trichloro-benzenes, a chloromethane The mixture of one or more in alkane, dichloromethane.
Using the method for the rare earth catalyst catalysis in olefine polymerization of above-mentioned nitrogen heterocyclic ring carbenes, with following feature： Under inert nitrogen gas or argon gas protection, organic solvent, temperature control is added to arrive in the polymer reactor for be dried deoxygenation by proportioning Polymerization temperature, opens stirring, and by monomer ratio olefinic monomer is added, and monomer mass percentage concentration is 5-30%, is subsequently adding dilute Native catalyst, rare earth catalyst component A is 1 with the mol ratio of component B, and rare earth catalyst consumption is mol ratio 50- of monomer/Ln 4000, polymerization temperature is -65 DEG C to 50 DEG C, and polymerization reaction time is 5min-180min；Using rubber post-processing approach to polymerization Thing is dried, and obtains polymerizate.Organic solvent is selected from pentane, hexane, heptane, hexamethylene, benzene,toluene,xylene, chlorine The mixture of one or more in benzene, dichloro-benzenes, trichloro-benzenes, monochloro methane, dichloromethane.
The rare earth catalyst of class nitrogen heterocyclic ring carbenes disclosed in this invention has following features：With generally report Tetrahydrofuran THF part compare, propylene, isobutyl can effectively be suppressed using the rare earth catalyst of nitrogen heterocyclic ring carbenes The chain transfer reaction of the class monomer of alkene one, successfully solves rare earth catalyst and is difficult to propylene, the difficulty of isobutene controllable polymerization Topic.The rare earth catalyst of nitrogen heterocyclic ring carbenes can be used for preparing higher molecular weight, the polypropylene of more narrow ditribution and third Alkene and alkene and the copolymer of alkene derivatives, prepare higher molecular weight, the rare earth EP rubbers of more narrow ditribution, functionalized rare earth Native EP rubbers；Higher molecular weight, the polyisobutene of more narrow ditribution and isobutene and alkene can be prepared and alkene is derivative The copolymer of thing, prepares higher molecular weight, the rare earth butyl rubber of more narrow ditribution, functionalization under higher polymeric reaction temperature Rare earth butyl rubber.
Specific embodiment
The present invention proposes following examples as further instruction, but not limits the model of the claims in the present invention protection Enclose.With the molecular weight and molecualr weight distribution index of gel permeation chromatograph (GPC) measure polymer, (weight average molecular weight is divided equally with number The ratio of sub- amount).
The preparation of the nitrogen heterocyclic ring cyclic carbine rear earth catalyst of embodiment 1
Different cyclopentadienyl parts, different N-heterocyclic carbines can be prepared using following methods：
(1) in glove box, ScCl is weighed3(15mmol) in being put into the Schlenk bottles for filling magnetic stir bar, add 50mL tetrahydrofurans.After closed Schlenk bottles, Schlenk bottles are taken out into glove box and is stirred overnight at 80 DEG C.After activating ScCl3(THF)3White suspension is brought in glove box, weighs LiCH2SiMe3(45mmol) dissolved with 15mL tetrahydrofurans, Slowly it is added drop-wise to ScCl3(THF)3In white suspension, 30min is reacted.Then, solvent THF is taken in decompression away, is adding 60mL just Hexane is extracted, and extract is freezed out and take advantage of after accessory substance cold filtration, is finally taken the n-hexane in filtrate away and is obtained white powder Sc(CH2SiMe3)3(THF)2。
(2) in glove box, Sc (CH are weighed2SiMe3)3(THF)2(7.25mmol) it is put into and fills magnetic stir bar In 100mL round-bottomed flasks, the n-hexane solvent dissolving of 10mL is added.Cyclopentadienyl part (7.25mmol) is weighed, it is molten with 1mL n-hexanes It is added drop-wise in reaction bulb under Xie Hou, room temperature.After 2h～48h is stirred at room temperature, reduced pressure concentration is put into -35 DEG C of refrigerator overnights, recrystallization Obtain the single cyclopentadienyl rare earth catalyst LSc (CH containing tetrahydrofuran part2SiMe3)2(THF)。
(3) in glove box, LSc (CH are weighed2SiMe3)2(THF) (2mmol) it is put into the 100ml that fills magnetic stir bar In round-bottomed flask, 10ml toluene solvants are added, dissolving is complete.N-heterocyclic carbine (2mmol) is weighed, after the dissolving of 5ml toluene, drop In adding to round-bottomed flask.2h is stirred at room temperature, reduced pressure concentration is put into -35 DEG C of refrigerator overnights, is recrystallized to give nitrogen heterocyclic ring Cabbeen and matches somebody with somebody Single cyclopentadienyl rare earth catalyst of body.
Cyclopentadienyl part can select cyclopentadienyl ligands, indenyl ligands, fluorenyl ligand, and nitrogen heterocycle carbine ligand can select miaow Oxazolyl Cabbeen, imidazolinyl Cabbeen, triazolyl Cabbeen, thiazolyl Cabbeen.
The polyacrylic preparation of embodiment 2
In glove box under inert nitrogen gas protection, 20ml toluene solutions are added in 100ml stainless steel cauldrons, Polymeric reaction temperature is controlled using constant temperature bath, polymeric reaction temperature is -30 DEG C, add propylene, propylene pressure to keep 0.1MPa, beat Stirring is opened, adds rare earth catalyst, the method provided using embodiment 1 to prepare rare earth catalyst, cyclopentadienyl part selects 1,3- Two (trimethyl silicon substrate) indenyl ligands (1,3- (Me3Si)2C9H5), nitrogen heterocycle carbine ligand selects 1,3- diisopropyl-imidazolium bases Cabbeen, rare earth catalyst Sc consumptions are 2umol, rare earth catalyst Sc and organoboron reagent [Ph3C][B(C6F5)4] mol ratio [Sc]/[B] is 1, after polymerisation 30min, adds methyl alcohol terminating reaction, and product is post-treated, vacuum drying, analysis test： Polyacrylic number-average molecular weight is 148.6 × 104G/mol, molecular weight distribution HI is 1.66.
The polyacrylic preparation of embodiment 3
Polymeric reaction temperature is -20 DEG C, and other polymeric reaction conditions are same as Example 2, analysis test：Polyacrylic number Average molecular weight is 123.9 × 104G/mol, molecular weight distribution HI is 1.49.
The polyacrylic preparation of embodiment 4
Polymeric reaction temperature is -40 DEG C, and other polymeric reaction conditions are same as Example 2, analysis test：Polyacrylic number Average molecular weight is 91.2 × 104G/mol, molecular weight distribution HI is 1.21.
The polyacrylic preparation of embodiment 5
Polymeric reaction temperature is -20 DEG C, and rare earth catalyst Sc consumptions are 5umol, other polymeric reaction conditions and embodiment 2 It is identical, analysis test：Polyacrylic number-average molecular weight is 94.9 × 104G/mol, molecular weight distribution HI is 1.57.
The polyacrylic preparation of embodiment 6
Polymeric reaction temperature is -10 DEG C, and cyclopentadienyl part selects trimethyl silicon substrate-tetramethyl-ring pentad ienyl ligands (C5Me4SiMe3), other polymeric reaction conditions are same as Example 2, analysis test：Polyacrylic number-average molecular weight be 56.2 × 104G/mol, molecular weight distribution HI is 1.65.
The preparation of the polyisobutene of embodiment 7
Polymeric reaction temperature is -35 DEG C, and polymerization reaction time is 60min, other polymeric reaction conditions and the phase of embodiment 2 Together, analysis test：The number-average molecular weight of polyisobutene is 39.8 × 104G/mol, molecular weight distribution HI is 1.52.
The preparation of the polyisobutene of embodiment 8
Polymeric reaction temperature is -5 DEG C, and polymerization reaction time is 120min, and cyclopentadienyl part selects 9- trimethyl silicon substrate fluorenyls Part (9-Me3SiC13H8), nitrogen heterocycle carbine ligand selects 1,3- dimethyl-imidazolidin base Cabbeens, other polymeric reaction conditions It is same as Example 2, analysis test：The number-average molecular weight of polyisobutene is 12.5 × 104G/mol, molecular weight distribution HI is 1.83。
The preparation of the polyethylene of embodiment 9
Polymeric reaction temperature is 20 DEG C, and cyclopentadienyl part selects trimethyl silicon substrate-tetramethyl-ring pentad ienyl ligands (C5Me4SiMe3), ethylene pressure keeps 0.15MPa, and other polymeric reaction conditions are same as Example 2, analysis test：Polyethylene Number-average molecular weight be 135.1 × 104G/mol, molecular weight distribution HI is 1.28.
The preparation of the polyethylene of embodiment 10
Polymeric reaction temperature is 45 DEG C, and ethylene pressure keeps 0.2MPa, and other polymeric reaction conditions are same as Example 2, Analysis test：The number-average molecular weight of polyethylene is 155.6 × 104G/mol, molecular weight distribution HI is 1.31.
The preparation of the propylene/ethylene copolymer of embodiment 11
Polymeric reaction temperature be -30 DEG C, propylene/ethylene monomeric charge mol ratio be 50/50, other polymeric reaction conditions with Embodiment 2 is identical, analysis test：The number-average molecular weight of propylene/ethylene copolymer is 56.8 × 104G/mol, molecular weight distribution HI For 1.58.
The preparation of 12 isobutenes of embodiment/isoprene copolymer
Polymeric reaction temperature is -35 DEG C, and isobutene/isoprene monomer molar ratio is 95/5, other polymerisations Condition is same as Example 2, analysis test：The number-average molecular weight of propylene/ethylene copolymer is 25.7 × 104G/mol, molecular weight Distribution HI is 1.68.
The preparation of 13 propylene/ethylenes of embodiment/norbornene copolymer
Polymeric reaction temperature is -15 DEG C, and propylene/ethylene/norbornene monomer molar ratio is 45/45/10, and other gather Close reaction condition same as Example 2, analysis test：The number-average molecular weight of propylene/ethylene/norbornene copolymer be 26.9 × 104G/mol, molecular weight distribution HI is 1.63.
The preparation of 14 propylene/ethylenes of embodiment/third component copolymer
Polymeric reaction temperature is 5 DEG C, and propylene/ethylene/third component monomeric charge mol ratio is 45/45/10, third component From to dimethyl amido styrene, cyclopentadienyl part selects trimethyl silicon substrate-tetramethyl-ring pentad ienyl ligands (C5Me4SiMe3), nitrogen heterocycle carbine ligand selects 1,3- dimethyl-triazolyl Cabbeen, other polymeric reaction conditions and embodiment 2 It is identical, analysis test：The number-average molecular weight of propylene/ethylene/third component copolymer is 16.7 × 104G/mol, molecular weight distribution HI is 1.86.

Claims (10)

1. the rare earth catalyst of a class nitrogen heterocyclic ring carbenes, it is characterised in that：Described rare earth catalyst includes A and B two Individual part；Described A is the rare earth compounding LMR of nitrogen heterocyclic ring Cabbeen coordination2X, wherein：L is cyclopentadienyl part, selected from ring penta 2 Alkenyl ligand, indenyl ligands, fluorenyl ligand；Described rare earth compounding, the structural formula of cyclopentadienyl part are as follows：R1、R2、R3、 R4And R5Selected from H, Me, Et, i-Pr, t-Bu, Ph, CH2Ph、SiMe3、CH2SiMe3, R1、R2、R3、R4And R5It is identical or different；M is Rare earth metal, selected from Sc, Y, Lu, Gd, Sm, Nd；R is the alkyl being joined directly together with rare earth metal, selected from CH2SiMe3、 CH2C6H4NMe2-o、CH2Ph、CH2CH=CH2、1,3-C3H4(Me)、1,3-C3H3(SiMe3)2、CH(SiMe3)2、Me、Et、i- Pr、t-Bu；X is nitrogen heterocyclic ring carbenes, selected from imidazole radicals Cabbeen, imidazolinyl Cabbeen, triazolyl Cabbeen, thiazolyl card Guest；Described B is organoboron reagent, selected from [Ph3C][B(C6F5)4]、[PhMe2NH][B(C6F5)4]、B(C6F5)3In one kind Or several mixtures；Described Me is methyl, Et is ethyl, Pr is propyl group, Bu is butyl, Ph is phenyl.
Rare earth compounding/cyclopentadienyl ligand structure formula.
2. rare earth catalyst according to claim 1, it is characterised in that：Described nitrogen heterocycle carbine ligand is selected from 1,3- bis- Methyl-imidazolyl Cabbeen, 1,3- diisopropyl-imidazolium base Cabbeens, 1,3- dimethyl-imidazolidin base Cabbeens, 1,3- diisopropyls- Imidazolinyl Cabbeen, 1,3- dimethyl-triazolyl Cabbeen, 1,3- diisopropyls-triazolyl Cabbeen, 1- methyl-thiazolyl Cabbeens, 1- isopropyls-thiazolyl Cabbeen.
3. rare earth catalyst according to claim 1 and 2, it is characterised in that：Described cyclopentadienyl part cyclopentadienyl Part is selected from C5H5、C5Me5、C5Me4SiMe3、C5HMe4、C5H2Me3、C5Me3(SiMe3)2、C5H3(SiMe3)2、C5Ph5；Wherein, Me is methyl, Ph is phenyl.
4. rare earth catalyst according to claim 1 and 2, it is characterised in that：Indenyl ligands choosing in described cyclopentadienyl part From 1-MeC9H6, 2-MeC9H6, 1- (Et) C9H6, 2- (Et) C9H6, 1- (t-Bu) C9H6, 1-Me3SiC9H6, 2- [3,5- (CF3)2C6H3]-C9H6, 2-C6H11-C9H6, 2- (3,5-Me2C6H3)-C9H6, 1-Me3Si-3-MeC9H5, 1-Me3Si-2-MeC9H5, 1- Me3Si-2-PhC9H5, 1-Me3Si-3-(Et)C9H5, 1-Me3Si-3-(t-Bu)C9H5, 1,3- (Me3Si)2C9H5, 1-Me3Si-3, 4,7-Me3C9H4, 1-Me3Si-2-Me-4-PhC9H4, 1,3- (Me3Si)2-2-MeC9H4, 2-Me-4,7-Me2C9H4, 2-Me-4, 6-Me2C9H4, 3-Me3Si-4,6-Me2C9H4, 1-Me3Si-2-Me-4,6-(i-Pr)2C9H3, 1-Me3Si-2-Me-4,7- Me2C9H3；Wherein, Me be methyl, Pr be propyl group, Et be ethyl, Bu be butyl, Ph be phenyl.
5. rare earth catalyst according to claim 3, it is characterised in that：Indenyl ligands are selected from 1- in described cyclopentadienyl part MeC9H6, 2-MeC9H6, 1- (Et) C9H6, 2- (Et) C9H6, 1- (t-Bu) C9H6, 1-Me3SiC9H6, 2- [3,5- (CF3)2C6H3]- C9H6, 2-C6H11-C9H6, 2- (3,5-Me2C6H3)-C9H6, 1-Me3Si-3-MeC9H5, 1-Me3Si-2-MeC9H5, 1-Me3Si-2- PhC9H5, 1-Me3Si-3-(Et)C9H5, 1-Me3Si-3-(t-Bu)C9H5, 1,3- (Me3Si)2C9H5, 1-Me3Si-3,4,7- Me3C9H4, 1-Me3Si-2-Me-4-PhC9H4, 1,3- (Me3Si)2-2-MeC9H4, 2-Me-4,7-Me2C9H4, 2-Me-4,6- Me2C9H4, 3-Me3Si-4,6-Me2C9H4, 1-Me3Si-2-Me-4,6-(i-Pr)2C9H3, 1-Me3Si-2-Me-4,7-Me2C9H3； Wherein, Me be methyl, Pr be propyl group, Et be ethyl, Bu be butyl, Ph be phenyl.
6. the rare earth catalyst according to claim 1 or 2 or 5, it is characterised in that：Fluorenyl ligand in described cyclopentadienyl part Selected from 2-MeC13H8, 9-MeC13H8, 9- (Et) C13H8,9- (i-Pr) C13H8, 9- (t-Bu) C13H8, 9-C6H11C13H8, 9- PhC13H8, 9- (2-MeC6H4)C13H8, 9- (2,4,6-Me3C6H2)C13H8, 9-Me3SiC13H8, 2,7- (t-Bu)2-C13H7, 2,7- (t-Bu)2-9-Me3SiC13H6；Wherein, Me be methyl, Pr be propyl group, Et be ethyl, Bu be butyl, Ph be phenyl.
7. rare earth catalyst according to claim 3, it is characterised in that：Fluorenyl ligand is selected from 2- in described cyclopentadienyl part MeC13H8, 9-MeC13H8, 9- (Et) C13H8,9- (i-Pr) C13H8, 9- (t-Bu) C13H8, 9-C6H11C13H8, 9-PhC13H8, 9- (2-MeC6H4)C13H8, 9- (2,4,6-Me3C6H2)C13H8, 9-Me3SiC13H8, 2,7- (t-Bu)2-C13H7, 2,7- (t-Bu)2-9- Me3SiC13H6；Wherein, Me be methyl, Pr be propyl group, Et be ethyl, Bu be butyl, Ph be phenyl.
8. using the method for the arbitrary described rare earth catalyst catalysis in olefine polymerization of claim 1-7, it is characterised in that：In inertia Under gas nitrogen or argon gas protection, organic solvent is added in the polymer reactor for be dried deoxygenation by proportioning, temperature control is to polymerization temperature Degree, opens stirring, and by monomer ratio olefinic monomer is added, and monomer mass percentage concentration is 5-30%, is subsequently adding rare earth catalyst Agent, rare earth catalyst component A is 1 with the mol ratio of component B, and rare earth catalyst consumption is mol ratio 50-4000 of monomer/Ln, Polymerization temperature is -65 DEG C to 50 DEG C, and polymerization reaction time is 5min-180min；Polymer is entered using rubber post-processing approach Row drying, obtains polymerizate；Polyolefinic number-average molecular weight is 10 × 104-180×104；Olefinic monomer selected from ɑ-alkene and The mixture of one or more in its derivative, conjugated alkene and its derivative, cyclenes hydrocarbons and their derivates；Alkene derivatives Selected from containing nitrogen, oxygen, chlorine, bromine atoms functional group alkene derivatives；Organic solvent selected from pentane, hexane, heptane, hexamethylene, The mixture of one or more in benzene,toluene,xylene, chlorobenzene, dichloro-benzenes, trichloro-benzenes, monochloro methane, dichloromethane.
9. rare earth catalyst catalysis in olefine polymerization method according to claim 8, it is characterised in that：The alkene is selected from second Alkene, propylene, n-butene, isobutene, butadiene, isoprene, laurene, styrene, ENB, dicyclopentadiene, oneself two The mixture of one or more in alkene.
10. rare earth catalyst catalysis in olefine polymerization method according to claim 8, it is characterised in that：The alkene derives Thing is selected from containing nitrogen, oxygen, chlorine, the ethene derivatives of bromine atoms functional group, butadiene derivatives, styrene derivative, norborneol The mixture of one or more in ene derivative.
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