CN103980399B - A kind of tropenyl rare-earth metal catalyst, preparation method and application - Google Patents
A kind of tropenyl rare-earth metal catalyst, preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of tropenyl rare-earth metal catalyst, preparation method and application, belong to catalyst field.The catalyst structure formula has two kinds.First, by the mixed solution of tropanol, glacial acetic acid and the concentrated sulfuric acid under nitrogen or argon atmosphere heating response for a period of time after, pH to 13~14 is adjusted, good solvent is added, organic phase is dried, filtering, take liquid to carry out air-distillation, collect 165~170 DEG C of components, or carry out vacuum distillation, 80~100 DEG C of components are collected, tropine alkene part is obtained；Secondly, tropine alkene part is added drop-wise in the solution dissolved with source metal, stirring reaction is filtered afterwards for a period of time at room temperature, concentrated, tropenyl rare-earth metal catalyst is obtained after recrystallization.The catalyst raw material is easy to get, available for alkene, alkynes, polar monomer homopolymerization and copolyreaction, or alkene, alkynes, polar monomer respectively with CO2Copolyreaction；The preparation method technique is simple, economic and environment-friendly, be adapted to industrialized production.
Description
Technical field
The present invention relates to a kind of tropenyl rare-earth metal catalyst, preparation method and application, belong to catalyst technology neck
Domain.
Background technology
At present, the catalyst system and catalyzing for being commercially used for alkene stereospecfic polymerization can be divided mainly into three major types, i.e. lithium-based catalyst, titanium
Series catalysts and rare earth series catalysts.Compared with traditional lithium system, Titanium series catalyst, rare-earth metal catalyst is homogeneous reaction,
System charging is easy, it is easy to accurate metering；Technique is simple, without catalyst deactivation and removing；Catalyst activity is high, consumption is few and
And be easily dispersed；Relative molecular mass distribution can easily be accommodated；Polymer gel content is low, content of ashes is few etc., thus rare earth gold
Metal catalyst is the mainstream development direction of current and following a period of time polymerisation.Especially there is the ring of smaller steric hindrance
Pentadienyl rare-earth metal catalyst generally shows higher cis Isosorbide-5-Nitrae-selectivity in isoprene homopolymerization, is mesh
The catalyst commonly used in preceding alkene stereospecfic polymerization.However, cyclopentadienyl group rare-earth metal catalyst is in isoprene homopolymerization
Middle catalytic activity has much room for improvement, and anti-in the copolymerization that cyclopentadienyl group rare-earth metal catalyst is catalyzed isoprene and ENB
In the copolymer of Ying Zhong, isoprene and ENB, the content of polyisoprene fragment is very low.
Compound of many with bioactivity is all using azabicyclo containing 8- [3.2.1] octane (tropane) basic structure as spy
Levy, such as the natural materials atropine in tropane alkaloidses, hyoscine and cocaine etc..With the intermediate product of atropine
Tropanol is tropine alkene made from raw material, can pass through the lone pair electrons on its nitrogen-atoms and the carbon atom and metal of 2~No. 4 positions
Atomic coordinate prepares metal organic complex.Hydrogen atom on the 2-4 positions carbon atom of tropine alkene molecule can obtain after sloughing
Tropine alkene anion, this anion can provide 2 σ-and 4 π-electron donor, can belong to class cyclopentadienyl ligands.Compare
Cyclopentadienyl-containing metal catalyst, tropenyl transition-metal catalyst shows higher activity in olefinic polymerization application.
Therefore, tropenyl metallic catalyst enters our visual field naturally as the substitute of cyclopentadienyl-containing metal catalyst.
Bergman et al. reports tropenyl transition-metal catalyst such as tropenyl titanium catalyst [(Tropidinyl) earliest
(C5H5)MCl2] (M=Ti, Zr) and tropenyl Zr catalyst [(Tropidinyl)2ZrCl2] answering in olefinic polyreaction
With.
In recent years, the preparation by the transient metal complex of part of tropenyl has caused the interest of people, because
The research of this respect helps to carry out part regioselectivity and stereoselectivity is further modified, and contributes to novel natural production
The exploitation and preparation of thing.The titanium that Stephan et al. reports a series of tropenyls-phosphinimide mixed ligand support is matched somebody with somebody
Compound [(Tropidinyl) (R3PN)TiCl2] (R=tBu,iPr), Matthias Tamm et al. report manganese class, ruthenium class tropine
Alkenyl metal complex.But the problem of syntheti c route of tropenyl metal complex has certain.Typically from tropine alkene list
Body sets out, and with n-BuLi, successive reaction generates tropine alkene in 3 days to slough the hydrogen atom on tropine alkene at -100~-70 DEG C
Base lithium salts.Then by the tropenyl lithium salts of generation and trimethyltin chloride (Me3SnCl) reaction obtains intermediate 1- trimethyls
Tin tropine alkene, adds transition metal halide reaction and obtains tropenyl metal complex.Although 1- tin trimethyl tropine alkene
It is easy to react with transition metal halide, but the reaction is also with generating poisonous volatile materials tin trimethyl halogenation
Thing, and overall reaction is time-consuming longer so that this method does not possess the possibility for adapting to heavy industrialization process, therefore, this area
Technical staff's exigence finds more economical, the environmentally friendly and suitable industrialized method for preparing tropenyl metal complex.
At present, tropenyl rare-earth metal catalyst, preparation method and its application in the polymerization not yet someone report.
The content of the invention
An object of the present invention is to provide a kind of tropenyl rare-earth metal catalyst；The second object of the present invention exists
In a kind of preparation method of tropenyl rare-earth metal catalyst of offer；The third object of the present invention is to provide a kind of tropine alkene
The application of base rare-earth metal catalyst.
The purpose of the present invention is realized by following technical scheme：
A kind of tropenyl rare-earth metal catalyst, the tropenyl rare-earth metal catalyst structural formula has following I, II
Two kinds：
Wherein, R1、R2And R11It is the initiation group being connected with rare earth metal；L1And L2It is the coordination being connected with rare earth metal
Group；R3、R4、R5、R12、R13、R14、R12′、R13' and R14' it is substituent on pi-allyl；R6、R7、R8、R9、R15、R16、R17、
R18、R15′、R16′、R17' and R18' it is substituent on tropenyl skeleton；R10、R19And R19' it is N originals in tropenyl skeleton
Substituted radical on son；Ln1And Ln2It is rare earth metal；
Wherein, R1、R2And R11Preferred alkyl, trimethyl silicon substrate, amido, imido grpup, alkoxy, benzyl, cyclopentadiene
One kind in base, indenyl, fluorenyl, F, Cl, Br and I；
L1And L2Preferred triphenyl phosphorus, tetrahydrofuran, ether, pyridine, imidazoles, carbazole, oxazole and dimethylformamide
(DMF) one kind in；
R3、R4、R5、R6、R7、R8、R9、R12、R13、R14、R12′、R13′、R14′R15、R16、R17、R18、R15′、R16′、R17' and
R18One kind in ' preferred hydrogen atom, methyl, ethyl, alkoxy, amino, itrile group and biotin；Wherein, R12And R12' identical,
R13And R13' identical, R14And R14' identical, R15And R15' identical, R16And R16' identical, R17And R17' identical, R18And R18' identical；
R10、R19And R19' preferred hydrogen atom, alkyl, alkoxy, phenyl, benzyl, amido, pyridine radicals, oxazolyl and life
One kind in thing element；R19And R19' identical；
Ln1And Ln2Preferred scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nb), promethium (Pm), samarium (Sm),
One kind in europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) and lutetium (Lu).
A kind of preparation method of tropenyl rare-earth metal catalyst, methods described step is as follows：
(1) tropine alkene part is prepared；
First, tropanol and glacial acetic acid are added separately in reactor, obtain mixed solution a, reactor is put into ice
In bath, under agitation, the concentrated sulfuric acid is added dropwise into mixed solution a, obtains mixed solution b；Wherein, tropanol, glacial acetic acid and
The mol ratio of the concentrated sulfuric acid is 1:1:2；
Secondly, the reactor equipped with mixed solution b is heated to 160~170 DEG C under nitrogen or argon atmosphere, instead
Answer after 20~24h and to take out reactor, be cooled to 20~25 DEG C, adjust pH to 13~14 with alkaline aqueous solution, obtain mixing molten
Liquid c；
Finally, 25~35mL good solvents 1 are added into mixed solution c, layering obtains aqueous phase and organic phase, into organic phase
Add after 5~10g solid driers, filtering takes liquid to carry out air-distillation, collects 165~170 DEG C of components, or depressurized
Distillation, collects 80~100 DEG C of components, obtains described tropine alkene part；
(2) tropenyl rare-earth metal catalyst is prepared；
First, reactor is placed in glove box, step (1) the tropine alkene part is added dropwise to dissolved with source metal
Solution in, under agitation react 25~40min, obtain mixed solution d；Wherein, reaction temperature is 20~25 DEG C, and tropine alkene is matched somebody with somebody
The mol ratio of body and source metal is 1:1；
Secondly, the mixed solution d is filtered, takes gained liquid to be concentrated, obtain tropenyl catalyzing of rare-earth metal
Agent crude product, tropenyl rare-earth metal catalyst of the present invention is obtained after the crude product is recrystallized；
Wherein, the preferred NaOH solution of step (1) the neutral and alkali aqueous solution；The preferred absolute ether of good solvent 1；Solid drier is excellent
Select anhydrous magnesium sulfate (MgSO4)；
Source metal preferably two tetrahydrofuran-three (trimethyl silicane methyl) rare earth compound (Ln in step (2)
(CH2SiMe3)3(THF)2)；The preferred scandiums of Ln, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and
One kind in lutetium；Me is methyl；THF is tetrahydrofuran.
A kind of application of tropenyl rare-earth metal catalyst, the tropenyl rare-earth metal catalyst is tried with alkyl aluminum
Agent and organic boron salt composition catalyst system and catalyzing, for branched-chain alkene, cycloolefin, alkynes, polar monomer homopolymerization, branch alkene
Hydrocarbon, cycloolefin, alkynes, the copolyreaction of polar monomer two of which, or branched-chain alkene, cycloolefin, alkynes, polar monomer difference
With CO2Copolyreaction；
Wherein, the mol ratio of organic boron salt, alkyllithium reagent and tropenyl rare-earth metal catalyst is 1~100:2~
100:1；Alkyllithium reagent is that molecular formula is AlX3Alkyl aluminum, molecular formula be HAlX2Alkyl-al hydride, molecular formula be
AlX2One kind in Cl alkyl aluminum chloride and aikyiaiurnirsoxan beta, X is alkyl；
The step of homopolymerization, is as follows：
Reactor is placed in glove box, tropenyl rare-earth metal catalyst, good solvent are sequentially added into reactor
2, alkyllithium reagent, reactant a, organic boron salt takes out reactor after reacting 0.3~72h under agitation, adds chain termination
Agent, makes the stopping of reaction；Reaction solution is settled with ethanol, separate out solid matter, by the solid matter at 30 DEG C vacuum
Dry, remove solvent to constant weight, obtain homopolymerization products；
Wherein, reactant a, alkyllithium reagent, the mol ratio of organic boron salt and tropenyl rare earth catalyst for 200~
5000:2~100:1~100:1；Reaction temperature is -30~90 DEG C；The consumption of good solvent 2 is 5~10mL；Reactant a is branch alkene
One kind in hydrocarbon, cycloolefin, alkynes or polar monomer.
The step of copolyreaction, is as follows：
Reactor is placed in glove box, tropenyl rare-earth metal catalyst, good solvent are sequentially added into reactor
2, alkyllithium reagent, reactant b or reactant c, organic boron salt takes out reactor after reacting 0.3~72h under agitation, plus
Enter chain terminating agent, make the stopping of reaction；Reaction solution is settled with ethanol, solid matter is separated out, by the solid matter 30
It is dried in vacuo at DEG C, removes solvent to constant weight, obtain copolymerization product；
Wherein, reactant b or reactant c, alkyllithium reagent, organic boron salt and the mol ratio of tropenyl rare earth catalyst
For 200~5000:200~5000:2~100:1~100:1；Reaction temperature is -30~90 DEG C；The consumption of good solvent 2 be 15~
25mL；Reactant b be branched-chain alkene, cycloolefin, alkynes, polar monomer in two kinds, reactant c be branched-chain alkene, cycloolefin,
One kind and CO in alkynes, polar monomer2；
It is the preferred trimethyl aluminium of alkyl aluminum, triethyl aluminum, tri-n-n-propyl aluminum, three n-butylaluminums, triisopropylaluminiuand, three different
Butyl aluminium, three hexyl aluminium, thricyclohexyl aluminium, trioctylaluminum, triphenyl aluminum, three p-methylphenyl aluminium, tribenzyl aluminium, ethyl dibenzyl
One kind in aluminium, ethyl di-p-tolyl aluminium and diethylbenzyl aluminium；
The alkyl-al hydride preferably hydrogenates dimethyl aluminium, diethyl aluminium hydride, hydrogenation diη-propyl aluminium, two positive fourths of hydrogenation
Base aluminium, hydrogenation diisopropyl aluminium, diisobutylaluminium hydride, hydrogenation diamyl aluminium, hydrogenation dihexyl aluminium, hydrogenation dicyclohexyl aluminium,
Hydrogenate dioctyl aluminium, hydrogenated diphenyl aluminium, hydrogenation di-p-tolyl aluminium, hydrogenation dibenzyl aluminium, ethyl hydride benzyl aluminium and hydrogenation
One kind in ethyl p-methylphenyl aluminium；
The preferred chlorodimethylalumiu of alkyl aluminum chloride, diethylaluminum chloride, chlorination diη-propyl aluminium, the positive fourth of chlorination two
Base aluminium, chlorination diisopropyl aluminium, di-isobutyl aluminum chloride, chlorination diamyl aluminium, chlorination dihexyl aluminium, chlorination dicyclohexyl aluminium,
Chlorination dioctyl aluminium, chlorinated diphenyl base aluminium, chlorination di-p-tolyl aluminium, chlorination dibenzyl aluminium, tonsilon benzyl aluminium and chlorination
One kind in ethyl p-methylphenyl aluminium；
One in the preferred MAO of aikyiaiurnirsoxan beta, ethylaluminoxane, n-propyl aikyiaiurnirsoxan beta and normal-butyl aikyiaiurnirsoxan beta
Kind；
Described (phenyl-pentafluoride) the boron salt ([Ph of the preferred triphenyl of organic boron salt (methyl)-four3C][B(C6F5)4]), phenyl-
(phenyl-pentafluoride) boron salt of dimethylamino-four ([PhMe2NH][B(C6F5)4]), phenyl-dimethyl amino-tetraphenyl boron salt
([PhMe2NH][BPh4]) and three (phenyl-pentafluoride) boron salt (B (C6F5)3) in one kind；
The branched-chain alkene optimal ethylene, propylene, 1- butylene, 1- amylenes, 4-methyl-1-pentene, 1- hexenes, 1- heptene,
1- octenes, 1- decene, 1- dodecylenes, tetradecene, cetene, 1- eicosylenes, styrene, Alpha-Methyl benzene second
Alkene, 3- 1-chloro-4-methyl-benzenes, 1,3- butadiene, isoprene, 1,3- cyclohexadiene, 1,5- pentadienes, 1,6- hexadienes and two
One kind in vinyl benzene；
The preferred ENB of cycloolefin, polarity ENB, norbornadiene, ethylidene norbornene, phenyl drop
One kind in bornylene, vinyl norbornene and dicyclopentadiene；
The preferred acetylene of described alkynes, phenylacetylene, to one kind in phenylacetylene and diacetylene aromatic hydrocarbons；
The preferred epoxyalkane of described polar monomer is oxirane, expoxy propane, 1,2- epoxy butanes, 2,3- epoxy fourths
Alkane, different epoxy butane, epoxychloropropane, epoxy bromopropane, methyl glycidyl ether, allyl glycidyl ether, butyl shrink
Glycerin ether, 2- ethyl hexylens glycidol ether, trifluoro-epoxy propane, 6-caprolactone, beta-butyrolactone, δ-valerolactone, lactide,
One kind in glycolide and 3- methyl-glycolide；
The ethanol of the chain terminating agent preferably di-tert-butyl-4-methy phenol Han 2,6-, using the volume of the ethanol as
100% meter, wherein, volume ratio shared by 2,6- di-tert-butyl-4-methy phenols is 5%；The preferred toluene of good solvent 2.
Beneficial effect
(1) tropenyl rare-earth metal catalyst of the present invention, is with a kind of common medicine intermediate tropanol
For initial feed, single step reaction is the part tropine alkene that is supported, and raw material is easy to get；
(2) the preparation method technique of tropenyl rare-earth metal catalyst of the present invention is simple, business efficiency is high, ring
Guaranteed cost is got well and is adapted to industrialized production；
(3) catalysis that tropenyl rare-earth metal catalyst of the present invention is constituted with alkyllithium reagent and organic boron salt
System, can be used in branched-chain alkene, cycloolefin, alkynes, the homopolymerization of polar monomer and branched-chain alkene, cycloolefin, alkynes, pole
The copolyreaction of property monomer two of which, or branched-chain alkene, cycloolefin, alkynes, polar monomer respectively with CO2Copolyreaction,
Obtain a series of new polymeric materials with specific structure；
(4) tropenyl rare-earth metal catalyst of the present invention, is that cyclopentadienyl-containing metal catalyst is replaced well
For thing, particularly single double alkyl catalysts of tropenyl scandium show high polymerization activity in isoprene polymerization reaction
(reach as high as 1.6 × 103kg·mol-1·h-1) and cis- Isosorbide-5-Nitrae-selectivity (100%), number-average molecular weight is 0.5~1,000,000 models
In enclosing, the molecular weight distribution with bimodal model, Mw/Mn=1.48~6.07；
(5) tropenyl rare-earth metal catalyst of the present invention, in isoprene and ENB copolymerization
In, polyisoprene contents are up to 91%, and what is finally obtained is the copolymer based on suitable Isosorbide-5-Nitrae-isoprene, and it is along Isosorbide-5-Nitrae-knot
Structure reaches as high as 88%, and report before this is all copolymer based on ENB, therefore this is a kind of not yet to report
New isoprene rubber material, the further research to its physicochemical property will be helpful to as the suitable application of its searching.
Brief description of the drawings
Fig. 1 is the crystal structure figure of the X-ray single crystal diffraction sign of single tropenyl scandium catalyst in embodiment 1；
Fig. 2 is the crystal structure figure of the X-ray single crystal diffraction sign of double tropenyl yttrium catalyst in embodiment 3；
Embodiment
The present invention, but not limited to this are described in detail with specific embodiment below in conjunction with the accompanying drawings.
The main agents information mentioned in following examples is shown in Table 1；Key instrument is shown in Table 2 with facility information.
Table 1
Table 2
Polymerization activity is by formula Activity=(myield)/(n in following examplescatTime) calculate.Its
In, Activity is polymerization activity, and unit is kgmol-1·h-1, m be branched-chain alkene, cycloolefin, alkynes, polar monomer or
CO2Quality, yield is yield, ncatFor the amount of catalyst material, time is the polymerization time used.
Polyisoprene microstructure can be by1H-NMR and13C-NMR spectrograms are provided, and it polymerize, and selectivity is specific to calculate public
Formula is as follows：
(1) selectivity (proportion) of 1,4- polyisoprene：
Mol1,4-IP%={ IH1/(IH1+0.5IH2)}*100
(2) selectivity (proportion) of 3,4- polyisoprene：
Mol3,4-IP%={ 0.5IH2/(IH1+0.5IH2)}*100
(3) selectivity (proportion) of cis- 1,4- polyisoprene：
Mol cis-1,4-IP%={ IC1/(IC1+IC2+IC3)}*100
(4) selectivity (proportion) of trans- 1,4- polyisoprene：
Mol trans-1,4-IP%={ IC1/(IC1+IC2+IC3)}*100
(5) selectivity (proportion) of 3,4- polyisoprene：
Mol3,4-IP%={ IC1/(IC1+IC2+IC3)}*100
Wherein, IP is polyisoprene, IH1For1Integration in H spectrums at 5.13ppm；IH2For1Product in H spectrums at 4.72ppm
Point；IC1For13Integration in C spectrums at 23.2ppm；IC2：Refer to13Integration in C spectrums at 18.5ppm；IC3：For1315.9ppm in C spectrums
The integration at place.
Embodiment 1
(1) tropine alkene part is prepared
First, tropanol 25.0g (177mmol) and glacial acetic acid 12g (11.5mL) are added separately in 250mL eggplants bottle,
Mixed solution a is obtained, eggplant bottle is put into ice bath, under agitation, concentrated sulfuric acid 46g (25mL) is added dropwise into mixed solution a,
Obtain mixed solution b；
Secondly, the eggplant bottle equipped with mixed solution b is heated to after 165 DEG C, reaction 22h under argon atmosphere by eggplant bottle
Take out, be cooled to 25 DEG C, adjust pH to 13 with NaOH solution, obtain the mixed solution c containing target product；
Finally, absolute ether (30ml) is added into mixed solution c, layering obtains aqueous phase and organic phase, into organic phase
Add anhydrous MgSO4After (8g), filtering takes liquid to carry out air-distillation, collects 165~170 DEG C of components, and cut is diluted with pentane
The raw material remained on a small quantity by a neutral alumina (Brockman Activity I) chromatographic column with removing afterwards.Final product
For colourless liquid, as tropine alkene part, yield is 49.1%, and purity is 99.8% ([M] by GC-MS detections+:123)。
(2) single tropenyl scandium catalyst is prepared
First, 25mL eggplants bottle is placed in glove box, tropine alkene part (0.308g, 2.5mmol) prepared by step (1)
It is added dropwise to dissolved with Sc (CH2SiMe3)3(THF)2In the hexane solution of (2.5mmol), 30min is reacted under agitation, is obtained
To mixed solution e；Wherein, reaction temperature is 25 DEG C；
Secondly, the mixed solution e is filtered, takes gained liquid to be concentrated, obtain single tropenyl scandium catalyst thick
Product, obtains yellow powder 0.695g, as shown in Figure 1, the yellow powder is single tropine after the crude product is recrystallized
Alkenyl scandium catalyst, yield is 65%.
Embodiment 2
(1) tropine alkene part is prepared
First, tropanol 25.0g (177mmol) and glacial acetic acid 12g (11.5mL) are added separately in 250mL eggplants bottle,
Mixed solution a is obtained, eggplant bottle is put into ice bath, under agitation, concentrated sulfuric acid 46g (25mL) is added dropwise into mixed solution a,
Obtain mixed solution b；
Secondly, the eggplant bottle equipped with mixed solution b is heated to eggplant bottle after 160 DEG C, reaction 20h under nitrogen atmosphere
Take out, be cooled to 20 DEG C, adjust pH to 14 with NaOH solution, obtain the mixed solution c containing target product；
Finally, absolute ether (25ml) is added into mixed solution c, layering obtains aqueous phase and organic phase, into organic phase
Add anhydrous MgSO4After (5g), filtering takes liquid to carry out vacuum distillation, collects 80~100 DEG C of components, and cut is diluted with pentane
The raw material remained on a small quantity by a neutral alumina (Brockman Activity I) chromatographic column with removing afterwards.Final product
For colourless liquid, as tropine alkene part, yield is 49.1%, and purity is 99.8% ([M] by GC-MS detections+:123)。
(2) tropenyl lutetium catalyst is prepared
First, 25mL eggplants bottle is placed in glove box, tropine alkene part (61.6mg, 0.5mmol) prepared by step (1)
It is added dropwise to dissolved with Lu (CH2SiMe3)3(THF)2In the hexane solution of (289mg, 0.5mmol), react under agitation
25min, obtains mixed solution f；Wherein, reaction temperature is 20 DEG C,
Secondly, the mixed solution f is concentrated, tropenyl lutetium catalyst crude product is obtained, by the crude product
Tropenyl lutetium catalyst is obtained after recrystallization, yield is 65%.
Embodiment 3
(1) tropine alkene part is prepared
First, tropanol 25.0g (177mmol) and glacial acetic acid 12g (11.5mL) are added separately in 250mL eggplants bottle,
Mixed solution a is obtained, eggplant bottle is put into ice bath, under agitation, concentrated sulfuric acid 46g (25mL) is added dropwise into mixed solution a,
Obtain mixed solution b；
Secondly, the eggplant bottle equipped with mixed solution b is heated to eggplant bottle after 170 DEG C, reaction 24h under nitrogen atmosphere
Take out, be cooled to 22 DEG C, adjust pH to 13 with NaOH solution, obtain the mixed solution c containing target product；
Finally, absolute ether (35ml) is added into mixed solution c, layering obtains aqueous phase and organic phase, into organic phase
Add anhydrous MgSO4After (10g), filtering takes liquid to carry out air-distillation, collects 165~170 DEG C of components, and cut is dilute with pentane
The raw material remained on a small quantity by a neutral alumina (Brockman Activity I) chromatographic column with removing after releasing.Final production
Thing is colourless liquid, as tropine alkene part, and yield is 49.1%, and purity is 99.8% ([M] by GC-MS detections+:123)。
(2) double tropenyl yttrium catalyst are prepared
First, by 25mL eggplants bottle be placed in glove box, by step (1) prepare tropine alkene part (0.616g, 5mmol) by
It is added dropwise to dissolved with Y (CH2SiMe3)3(THF)2In the hexane solution of (1.231g, 2.5mmol), react under agitation
40min, obtains mixed solution h；Wherein, reaction temperature is 23 DEG C；
Secondly, the mixed solution h is filtered, takes gained liquid to be concentrated, obtain double tropenyl yttrium catalyst thick
Product, obtains dark orange powder 1.044g, as shown in Figure 2, dark orange powder is double bracket product after the crude product is recrystallized
Alkenyl yttrium catalyst, yield is 80%.
Example 4 below~embodiment 24 is the application of single tropenyl scandium catalyst described in embodiment 1.
Embodiment 4
50mL eggplants bottle is placed in glove box, 25 μm of ol tropenyl scandium catalyst, 5mL first are sequentially added into eggplant bottle
Benzene, 50 μm of ol AlMe3, 5mmol isoprene and 25 μm of ol [Ph3C][B(C6F5)4], will after stirring reaction 24h at -30 DEG C
Eggplant bottle takes out, and adds the ethanol of 30mL di-tert-butyl-4-methy phenols Han 2,6-, makes the stopping of reaction, wherein, with the ethanol
Volume is 100% meter, and volume ratio shared by 2,6- di-tert-butyl-4-methy phenols is 5%；Reaction solution is settled with ethanol,
White solid matter is separated out, the solid matter is dried in vacuo at 30 DEG C, solvent is removed to constant weight, obtains poly- isoamyl two
Alkene, net weight 0.34g, conversion ratio 100%, polymerization activity is 0.57kgmol-1·h-1；The number of gpc analysis polyisoprene is equal
Molecular weight Mn=13 × 103, molecular weight distribution Mw/Mn=5.24；Cis- 1,4- polymerizations selectivity 100%.
Embodiment 5
50mL eggplants bottle is placed in glove box, 25 μm of ol tropenyl scandium catalyst, 5mL first are sequentially added into eggplant bottle
Benzene, 50 μm of ol AlMe3, 15mmol isoprene and 25 μm of ol [Ph3C][B(C6F5)4], reaction time 0.3h, reaction temperature 25
DEG C, remaining operation be the same as Example 4 obtains polyisoprene, net weight 1.02g, conversion ratio 100%, and polymerization activity is 1.2 ×
102kg·mol-1·h-1；The number-average molecular weight M of gpc analysis polyisoprenen=10 × 103, molecular weight distribution Mw/Mn=
6.07；Cis- 1,4- polymerizations selectivity 99%.
Embodiment 6
250mL eggplants bottle is placed in glove box, 25 μm of ol tropenyl scandium catalyst, 5mL first are sequentially added into eggplant bottle
Benzene, 50 μm of ol AlMe3, 125mmol isoprene and 25 μm of ol [Ph3C][B(C6F5)4], reaction time 0.3h, reaction temperature 25
DEG C, remaining operation be the same as Example 4 obtains polyisoprene, net weight 6.81g, conversion ratio 80%, and polymerization activity is 1.6 ×
103kg·mol-1·h-1；The number-average molecular weight M of gpc analysis polyisoprenen=15 × 103, molecular weight distribution Mw/Mn=
4.96；Cis- 1,4- polymerizations selectivity 98%.
Embodiment 7
50mL eggplants bottle is placed in glove box, 25 μm of ol tropenyl scandium catalyst, 10mL first are sequentially added into eggplant bottle
Benzene, 2.5mmol AliBu3, 5mmol isoprene and 2.5mmol [PhNHMe2][B(C6F5)4], reaction time 72h, reaction temperature
25 DEG C of degree, remaining operation be the same as Example 4, obtains polyisoprene, net weight 0.59g, conversion ratio 90%, and polymerization activity is 4.1 ×
10kg·mol-1·h-1；The number-average molecular weight M of gpc analysis polyisoprenen=9 × 103, molecular weight distribution Mw/Mn=5.55；
Cis- 1,4- polymerizations selectivity 99%.
Embodiment 8
50mL eggplants bottle is placed in glove box, 25 μm of ol tropenyl scandium catalyst, 5mL first are sequentially added into eggplant bottle
Benzene, 50 μm of ol AlMe3, 5mmol isoprene and 25 μm of ol [Ph3C][B(C6F5)4], reaction time 5h, 90 DEG C of reaction temperature,
Remaining operation be the same as Example 4, obtains polyisoprene, net weight 0.34g, and conversion ratio 100%, polymerization activity is 2.3kgmol-1·h-1；The number-average molecular weight M of gpc analysis polyisoprenen=9 × 104, molecular weight distribution Mw/Mn=1.48；Cis- 1,4- gathers
Close selectivity 85%.
Embodiment 9
50mL eggplants bottle is placed in glove box, 25 μm of ol tropenyl scandium catalyst, 5mL first are sequentially added into eggplant bottle
Benzene, 50 μm of ol AliBu3, 5mmol phenylacetylenes and 25 μm of ol [PhNHMe2][B(C6F5)4], reaction time 0.3h, reaction temperature 50
DEG C, remaining operation be the same as Example 4 obtains polyphenylacetylene, net weight 0.51g, conversion ratio 100%.The number of gpc analysis polyphenylacetylene is equal
Molecular weight Mn=10 × 103, molecular weight distribution Mw/Mn=2.13.
Embodiment 10
50mL eggplants bottle is placed in glove box, 25 μm of ol tropenyl scandium catalyst, 7mL first are sequentially added into eggplant bottle
Benzene, 50 μm of ol AliBu3, 5mmol D, L- lactides and 25 μm of ol [PhNHMe2][B(C6F5)4], reaction time 2.5h, reaction
25 DEG C of temperature, remaining operation be the same as Example 4, obtains PDLLA, net weight 0.63g, conversion ratio 87%.The poly- D of gpc analysis,
The number-average molecular weight M of L- lactidesn=9 × 104, molecular weight distribution Mw/Mn=2.55.
Embodiment 11
50mL eggplants bottle is placed in glove box, 25 μm of ol tropenyl scandium catalyst, 10mL first are sequentially added into eggplant bottle
Benzene, 1.2mmol AlMe3, 5mmol 6-caprolactones and 1.2mmol [Ph3C][B(C6F5)4], reaction time 2.5h, reaction temperature 25
DEG C, remaining operation be the same as Example 4 obtains poly-epsilon-caprolactone, net weight 0.43g, conversion ratio 75%；Gpc analysis poly-epsilon-caprolactone
Number-average molecular weight Mn=6 × 104, molecular weight distribution Mw/Mn=2.58.
Embodiment 12
50mL eggplants bottle is placed in glove box, 25 μm of ol tropenyl scandium catalyst, 5mL first are sequentially added into eggplant bottle
Benzene, 50 μm of ol AlMe3, 5mmol expoxy propane and 25 μm of ol [Ph3C][B(C6F5)4], reaction time 5h, 50 DEG C of reaction temperature,
Remaining operation be the same as Example 4, obtains PPOX, net weight 0.26g, conversion ratio 90%；The number of gpc analysis PPOX is equal
Molecular weight Mn=13 × 104, molecular weight distribution Mw/Mn=2.62.
Embodiment 13
50mL eggplants bottle is placed in glove box, 21 μm of ol tropenyl scandium catalyst, 25mL first are sequentially added into eggplant bottle
Benzene, 42 μm of ol AliBu3, 5mmol isoprene, 2.5mmol ENBs and 21 μm of ol [Ph3C][B(C6F5)4], at 25 DEG C
Eggplant bottle is taken out after stirring reaction 2h, the ethanol of 30mL di-tert-butyl-4-methy phenols Han 2,6- is added, makes the stopping of reaction, its
In, counted using the volume of the ethanol as 100%, volume ratio shared by 2,6- di-tert-butyl-4-methy phenols is 5%；By reaction solution
Settled with ethanol, separate out solid matter, the solid matter is dried in vacuo at 30 DEG C, removed solvent to constant weight, obtain
To isoprene and the copolymer of ENB, the number-average molecular weight M of gpc analysis copolymern=12 × 103, molecular weight distribution
Mw/Mn=2.91；Isoprene and ENB ratio are 91 in copolymer:9, the cis- Isosorbide-5-Nitrae in polyisoprene part-polymerization selection
Property is 88%.
Embodiment 14
50mL eggplants bottle is placed in glove box, 21 μm of ol tropenyl scandium catalyst, 25mL first are sequentially added into eggplant bottle
Benzene, 42 μm of ol AliBu3, 5mmol isoprene, 5mmol styrene and 21 μm of ol [Ph3C][B(C6F5)4], reaction time 72h,
- 30 DEG C of reaction temperature, remaining operation be the same as Example 13, obtains the copolymer of isoprene and styrene, conversion ratio is 93%；
The number-average molecular weight M of gpc analysis copolymern=4 × 103, molecular weight distribution Mw/Mn=2.29.
Embodiment 15
50mL eggplants bottle is placed in glove box, 21 μm of ol tropenyl scandium catalyst, 25mL first are sequentially added into eggplant bottle
Benzene, 42 μm of ol AliBu3, 5mmol isoprene, 5mmol1,3- cyclohexadiene and 21 μm of ol [Ph3C][B(C6F5)4], during reaction
Between 2h, 25 DEG C of reaction temperature, remaining operation be the same as Example 13 obtains isoprene and 1, the copolymer of 3- cyclohexadiene is converted
Rate is 90%；The number-average molecular weight M of gpc analysis copolymern=12 × 103, molecular weight distribution Mw/Mn=2.45.
Embodiment 16
50mL eggplants bottle is placed in glove box, 21 μm of ol tropenyl scandium catalyst, 25mL first are sequentially added into eggplant bottle
Benzene, 42 μm of ol AliBu3, 15mmol ENBs, 5mmol styrene, and 21 μm of ol [Ph3C][B(C6F5)4], the reaction time
0.3h, 90 DEG C of reaction temperature, remaining operation be the same as Example 13 obtains the copolymer of ENB and styrene, conversion ratio is
100%；The number-average molecular weight M of gpc analysis copolymern=4 × 104, molecular weight distribution Mw/Mn=2.20.
Embodiment 17
250mL eggplants bottle is placed in glove box, 21 μm of ol tropenyl scandium catalyst, 25mL first are sequentially added into eggplant bottle
Benzene, 42 μm of ol AliBu3, 105mmol ENBs, 105mmol1,3- cyclohexadiene, and 21 μm of ol [Ph3C][B(C6F5)4],
Reaction time 3h, 25 DEG C of reaction temperature, remaining operation be the same as Example 13 obtains ENB and 1, the copolymerization of 3- cyclohexadiene
Thing, conversion ratio is 97%；The number-average molecular weight M of gpc analysis copolymern=3 × 104, molecular weight distribution Mw/Mn=2.61.
Embodiment 18
250mL eggplants bottle is placed in glove box, 21 μm of ol tropenyl scandium catalyst, 25mL first are sequentially added into eggplant bottle
Benzene, 42 μm of ol AliBu3, 53mmol ENBs, 53mmol1,4- butadiene, and 21 μm of ol [Ph3C][B(C6F5)4], reaction
Time 3h, 25 DEG C of reaction temperature, remaining operation be the same as Example 13 obtains the copolymer of ENB and Isosorbide-5-Nitrae-butadiene, converted
Rate is 90%；The number-average molecular weight M of gpc analysis copolymern=4.2 × 104, molecular weight distribution Mw/Mn=1.69.
Embodiment 19
50mL eggplants bottle is placed in glove box, 21 μm of ol tropenyl scandium catalyst, 25mL first are sequentially added into eggplant bottle
Benzene, 2.1mmol AliBu3, 5mmol ENBs, 5mmol dicyclopentadienes, and 2.1mmol [Ph3C][B(C6F5)4], reaction
Time 50h, 25 DEG C of reaction temperature, remaining operation be the same as Example 13 obtains the copolymer of ENB and dicyclopentadiene, converted
Rate is 95%；The number-average molecular weight M of gpc analysis copolymern=3.8 × 104, molecular weight distribution Mw/Mn=3.37.
Embodiment 20
50mL eggplants bottle is placed in glove box, 21 μm of ol tropenyl scandium catalyst, 25mL first are sequentially added into eggplant bottle
Benzene, 1.2mmol AliBu3, 5mmol isoprene, 5mmol1,4- butadiene, and 1.2mmol [Ph3C][B(C6F5)4], reaction
Time 3h, 90 DEG C of reaction temperature, remaining operation be the same as Example 13 obtains the copolymer of isoprene and Isosorbide-5-Nitrae-butadiene, converted
Rate is 99%；The number-average molecular weight M of gpc analysis copolymern=4 × 104, molecular weight distribution Mw/Mn=1.77.
Embodiment 21
50mL eggplants bottle is placed in glove box, 21 μm of ol tropenyl scandium catalyst, 25mL first are sequentially added into eggplant bottle
Benzene, 42 μm of ol AliBu3, 5mmol isoprene, 5mmol dicyclopentadienes, and 21 μm of ol [Ph3C][B(C6F5)4], during reaction
Between 3h, -30 DEG C of reaction temperature, remaining operation be the same as Example 13, obtain the copolymer of isoprene and dicyclopentadiene, conversion ratio
For 90%；The number-average molecular weight M of gpc analysis copolymern=15 × 104, molecular weight distribution Mw/Mn=1.29.
Embodiment 22
50mL eggplants bottle is placed in glove box, 21 μm of ol tropenyl scandium catalyst, 20mL first are sequentially added into eggplant bottle
Benzene, 42 μm of ol AliBu3, 5mmol oxirane, 5mmol expoxy propane, and 21 μm of ol [Ph3C][B(C6F5)4], the reaction time
3h, 50 DEG C of reaction temperature, remaining operation be the same as Example 13 obtains the copolymer of oxirane and expoxy propane, conversion ratio is
99%；The number-average molecular weight M of gpc analysis copolymern=9 × 104, molecular weight distribution Mw/Mn=1.59.
Embodiment 23
50mL eggplants bottle is placed in glove box, 21 μm of ol tropenyl scandium catalyst, 15mL first are sequentially added into eggplant bottle
Benzene, 42 μm of ol AliBu3, 5mmol D, L- lactides, 5mmol 6-caprolactones, and 21 μm of ol [Ph3C][B(C6F5)4], during reaction
Between 3h, 25 DEG C of reaction temperature, remaining operation be the same as Example 13, obtain D, L- lactides and 6-caprolactone copolymer, conversion ratio
For 98%；The number-average molecular weight M of gpc analysis copolymern=8 × 104, molecular weight distribution Mw/Mn=1.49.
Embodiment 24
100ml reactors are placed in glove box, 0.05mol tropenyl scandium catalyst is sequentially added into reactor,
1mL toluene, 0.1mol AliBu3, 20mol expoxy propane, 0.05mol [Ph3C][B(C6F5)4], reactor is sealed, transfer is sold
Casing, CO is passed through into reactor2, regulation pressure reacts 24 hours at 70 DEG C to 6MPa, is cooled to 25 DEG C, molten with chloroform
Solution, reaction solution is settled with ethanol, separates out white solid matter, the solid matter is dried in vacuo at 30 DEG C, removed
Go solvent to constant weight, obtain expoxy propane and CO2Copolymer；Yield is 23.0%, and molecular weight is Mn=41.0 × 103, molecule
Amount distribution Mw/Mn=2.0.
The present invention include but is not limited to above example, it is every carried out under the principle of spirit of the present invention it is any equivalent
Replace or local improvement, all will be regarded as within protection scope of the present invention.
Claims (8)
1. a kind of preparation method of tropenyl rare-earth metal catalyst, it is characterised in that：The tropenyl rare earth metal is urged
Agent structural formula has following I, II two kind：
Wherein, R1、R2And R11It is the initiation group being connected with rare earth metal；L1And L2It is the coordinating group being connected with rare earth metal；
R3、R4、R5、R12、R13、R14、R12′、R13' and R14' it is substituent on pi-allyl；R6、R7、R8、R9、R15、R16、R17、R18、
R15′、R16′、R17' and R18' it is substituent on tropenyl skeleton；R10、R19And R19' it is in tropenyl skeleton on N atoms
Substituted radical；Ln1And Ln2It is rare earth metal；
Methods described step is as follows：
(1) tropine alkene part is prepared；
First, tropanol and glacial acetic acid are added separately in reactor, obtain mixed solution a, reactor is put into ice bath,
Under agitation, the concentrated sulfuric acid is added dropwise into mixed solution a, obtains mixed solution b；Wherein, tropanol, glacial acetic acid and the concentrated sulfuric acid
Mol ratio be 1:1:2；
Secondly, the reactor equipped with mixed solution b is heated to 160~170 DEG C, reaction 20 under nitrogen or argon atmosphere
Reactor is taken out after~24h, 20~25 DEG C are cooled to, pH is adjusted to 13~14 with alkaline aqueous solution, obtains mixed solution c；
Finally, 25~30mL good solvents 1 are added into mixed solution c, layering obtains aqueous phase and organic phase, is added into organic phase
After 5~10g solid driers, filtering takes liquid to carry out air-distillation, collects 165~170 DEG C of components, or progress vacuum distillation,
80~100 DEG C of components are collected, described tropine alkene part is obtained；
(2) tropenyl rare-earth metal catalyst is prepared；
First, reactor is placed in glove box, step (1) the tropine alkene part is added dropwise to dissolved with the molten of source metal
In liquid, 25~40min is reacted under agitation, mixed solution d is obtained；Wherein, reaction temperature be 20~25 DEG C, tropine alkene part with
The mol ratio of source metal is 1:1；
Secondly, the mixed solution d is filtered, takes gained liquid to be concentrated, obtain tropenyl rare-earth metal catalyst thick
Product, tropenyl rare-earth metal catalyst is obtained after the crude product is recrystallized.
2. a kind of preparation method of tropenyl rare-earth metal catalyst according to claim 1, it is characterised in that：
R1、R2And R11Be alkyl, trimethyl silicon substrate, amido, imido grpup, alkoxy, benzyl, cyclopentadienyl group, indenyl, fluorenyl,
One kind in F, Cl, Br and I；
R3、R4、R5、R6、R7、R8、R9、R12、R13、R14、R12′、R13′、R14′、R15、R16、R17、R18、R15′、R16′、R17' and R18′
It is one kind in hydrogen atom, methyl, ethyl, alkoxy, amino, itrile group and biotin；Wherein, R12And R12' identical, R13With
R13' identical, R14And R14' identical, R15And R15' identical, R16And R16' identical, R17And R17' identical, R18And R18' identical；
R10、R19And R19' it is hydrogen atom, alkyl, alkoxy, phenyl, benzyl, amido, pyridine radicals, oxazolyl and biotin
One kind；R19And R19' identical.
3. a kind of preparation method of tropenyl rare-earth metal catalyst according to claim 1, it is characterised in that：
L1And L2It is one kind in triphenyl phosphorus, tetrahydrofuran, ether, pyridine, imidazoles, carbazole, oxazole and DMF；Ln1And Ln2
It is one kind in scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.
4. a kind of preparation method of tropenyl rare-earth metal catalyst according to any one of claims 1 to 3, its feature
It is：Step (1) neutral and alkali aqueous solution is NaOH solution；Good solvent 1 is absolute ether；Solid drier is anhydrous magnesium sulfate；
Source metal is two tetrahydrofuran-three (trimethyl silicane methyl) rare earth compounds in step (2), and molecular formula is Ln
(CH2SiMe3)3(THF)2), the Ln is scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium
In one kind；Me is methyl；THF is tetrahydrofuran.
5. tropenyl rare-earth metal catalyst made from a kind of preparation method as described in any one of claims 1 to 3 should
With, it is characterised in that：The tropenyl rare-earth metal catalyst and alkyllithium reagent and organic boron salt composition catalyst system and catalyzing, are used
In branched-chain alkene, cycloolefin, alkynes, polar monomer homopolymerization, branched-chain alkene, cycloolefin, alkynes, polar monomer wherein two
Kind copolyreaction, or branched-chain alkene, cycloolefin, alkynes, polar monomer respectively with CO2Copolyreaction；
Wherein, the mol ratio of organic boron salt, alkyllithium reagent and tropenyl rare-earth metal catalyst is 1~100:2~100:
1；Alkyllithium reagent is that molecular formula is AlX3Alkyl aluminum, molecular formula be HAlX2Alkyl-al hydride, molecular formula be AlX2Cl's
One kind in alkyl aluminum chloride and aikyiaiurnirsoxan beta, X is alkyl；
The step of homopolymerization, is as follows：
Reactor is placed in glove box, tropenyl rare-earth metal catalyst, good solvent 2, alkane are sequentially added into reactor
Base aluminon, reactant a, organic boron salt takes out reactor after reacting 0.3~72h under agitation, adds chain terminating agent, makes
The stopping of reaction；Reaction solution is settled with ethanol, solid matter is separated out, the solid matter is dried in vacuo at 30 DEG C,
Solvent is removed to constant weight, homopolymerization products are obtained；
Wherein, the mol ratio of reactant a, alkyllithium reagent, organic boron salt and tropenyl rare earth catalyst is 200~5000:2
~100:1~100:1；Reaction temperature is -30~90 DEG C；The consumption of good solvent 2 is 5~10mL；Reactant a is branched-chain alkene, ring
One kind in alkene, alkynes or polar monomer.
6. a kind of application of tropenyl rare-earth metal catalyst according to claim 5, it is characterised in that：The copolymerization
The step of reaction, is as follows：
Reactor is placed in glove box, tropenyl rare-earth metal catalyst, good solvent 2, alkane are sequentially added into reactor
Base aluminon, reactant b or reactant c, organic boron salt take out reactor after reacting 0.3~72h under agitation, add chain
Terminator, makes the stopping of reaction；Reaction solution is settled with ethanol, solid matter is separated out, by the solid matter at 30 DEG C
Vacuum drying, removes solvent to constant weight, obtains copolymerization product；
Wherein, reactant b or reactant c, alkyllithium reagent, organic boron salt and the mol ratio of tropenyl rare earth catalyst are
200~5000:200~5000:2~100:1~100:1；Reaction temperature is -30~90 DEG C；The consumption of good solvent 2 be 15~
25mL；Reactant b be branched-chain alkene, cycloolefin, alkynes, polar monomer in two kinds, reactant c be branched-chain alkene, cycloolefin,
One kind and CO in alkynes, polar monomer2。
7. a kind of application of tropenyl rare-earth metal catalyst according to claim 6, it is characterised in that：
The alkyl aluminum is trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, three n-butylaluminums, triisopropylaluminiuand, triisobutyl
Aluminium, three hexyl aluminium, thricyclohexyl aluminium, trioctylaluminum, triphenyl aluminum, three p-methylphenyl aluminium, tribenzyl aluminium, three n-butylaluminum,
One kind in ethyl di-p-tolyl aluminium and diethylbenzyl aluminium；
The alkyl-al hydride is hydrogenation dimethyl aluminium, diethyl aluminium hydride, hydrogenation diη-propyl aluminium, hydrogenation di-n-butyl aluminium,
Hydrogenate diisopropyl aluminium, diisobutylaluminium hydride, hydrogenation diamyl aluminium, hydrogenation dihexyl aluminium, hydrogenation dicyclohexyl aluminium, hydrogenation two
Octyl group aluminium, hydrogenated diphenyl aluminium, hydrogenation di-p-tolyl aluminium, hydrogenation dibenzyl aluminium, ethyl hydride benzyl aluminium and ethyl hydride pair
One kind in tolyl aluminium；
The alkyl aluminum chloride be chlorodimethylalumiu, diethylaluminum chloride, chlorination diη-propyl aluminium, chlorination di-n-butyl aluminium,
Chlorination diisopropyl aluminium, di-isobutyl aluminum chloride, chlorination diamyl aluminium, chlorination dihexyl aluminium, chlorination dicyclohexyl aluminium, chlorination two
Octyl group aluminium, chlorinated diphenyl base aluminium, chlorination di-p-tolyl aluminium, chlorination dibenzyl aluminium, tonsilon benzyl aluminium and tonsilon pair
One kind in tolyl aluminium；
The aikyiaiurnirsoxan beta is one kind in MAO, ethylaluminoxane, n-propyl aikyiaiurnirsoxan beta and normal-butyl aikyiaiurnirsoxan beta；
Described organic boron salt is triphenyl (methyl)-four (phenyl-pentafluoride) boron salt, phenyl-dimethyl amino-four (phenyl-pentafluoride) boron
One kind in salt, phenyl-dimethyl amino-tetraphenyl boron salt and three (phenyl-pentafluoride) boron salts；
The branched-chain alkene be ethene, propylene, 1- butylene, 1- amylenes, 4-methyl-1-pentene, 1- hexenes, 1- heptene, 1- octenes,
1- decene, 1- dodecylenes, tetradecene, cetene, 1- eicosylenes, styrene, α-methylstyrene, 3- chloromethanes
One kind in base styrene, 1,3- butadiene, isoprene, 1,5- pentadienes, 1,6- hexadienes and divinylbenzene；
The cycloolefin be ENB, polarity ENB, norbornadiene, ethylidene norbornene, phenyl norbornene,
One kind in vinyl norbornene and dicyclopentadiene；
Described alkynes is acetylene, phenylacetylene, to one kind in phenylacetylene and diacetylene aromatic hydrocarbons；
Described polar monomer is oxirane, expoxy propane, 1,2- epoxy butanes, 2,3- epoxy butanes, different epoxy butane, ring
Oxygen chloropropane, epoxy bromopropane, methyl glycidyl ether, allyl glycidyl ether, butyl glycidyl ether, 2- ethyls it is sub- oneself
Base glycidol ether, trifluoro-epoxy propane, 6-caprolactone, beta-butyrolactone, δ-valerolactone, lactide, glycolide and 3- methyl-second
One kind in lactide；
8. a kind of application of tropenyl rare-earth metal catalyst according to claim 6, it is characterised in that：The chain is whole
Only agent is the ethanol of the di-tert-butyl-4-methy phenol containing 2,6-, is counted using the volume of ethanol as 100%, wherein, 2,6- bis- tertiary fourths
Volume ratio shared by base -4- methylphenols is 5%；Good solvent 2 is toluene.
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