CN104592425B - A kind of cycloheptatriene base rare-earth metal catalyst, preparation method and application - Google Patents
A kind of cycloheptatriene base rare-earth metal catalyst, preparation method and application Download PDFInfo
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- CN104592425B CN104592425B CN201510059201.3A CN201510059201A CN104592425B CN 104592425 B CN104592425 B CN 104592425B CN 201510059201 A CN201510059201 A CN 201510059201A CN 104592425 B CN104592425 B CN 104592425B
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Abstract
The invention discloses a kind of cycloheptatriene base rare-earth metal catalyst, preparation method and application, belong to catalyst field.Methods described step is as follows:First, tropolone, paratoluensulfonyl chloride and triethylamine are added in reactor, under nitrogen atmosphere reaction a period of time, then amido substituent are added thereto, reaction overnight, after recrystallization obtains pure products, and Et3OBF4Solution reaction a few houres after, then Deca amido substituent, be stirred overnight, column chromatography purification obtains cycloheptatriene ylidene ligands;Secondly, part is added drop-wise to dissolved with LnR3Toluene solution in, under room temperature, stirring reaction filters for a period of time afterwards, concentrate, after recrystallization cycloheptatriene base rare-earth metal catalyst.Described catalyst raw material is easy to get, and may be used on the polyreaction of various of monomer, including alkene, alkynes, the homopolymerization of polar monomer and copolymerization, or respectively with CO2Copolyreaction;Described method for preparing catalyst is simple, economic and environment-friendly, applied range, suitable industrialized production.
Description
Technical field
The present invention relates to a kind of cycloheptatriene base rare-earth metal catalyst, preparation method and application, belong to catalyst technology
Field.
Background technology
Conjugation refers to make the pi-electron (or p electronics) in system in conjugated system due to interatomic influencing each other
It is distributed a kind of electronic effect changing, be a kind of important electronic effect in organic chemistry.It can make electron cloud in molecule
The distribution of density changes (copline), and interior energy reduces, and bond distance tends to equalizing, and refractive index raises, and whole molecule more becomes
Stable.Structure for these molecules and its property Quality Research, all have very important significance with practicality in theory, because
This this kind of compound causes the broad interest of people.
Cycloheptatriene ylidene ligands have been widely used in field of coordinative chemistry as non-cyclopentadienyl class part.This part is high
10 pi-electron systems of degree conjugation, have started the frontier of non-benzenoid aromatic compound.In recent years, with cycloheptatriene base for joining
The preparation of the transient metal complex of body is subject to the extensive concern of scientists all the time.Saman Damavandi et al. is
Early report application in olefinic polyreaction for the cycloheptatriene base transition titanium metal catalyst, for catalyzed ethylene polymerization.
Philip J.Bailey research group has synthesized the cycloheptatriene base metallo-organic compound of magnesium, aluminum and indium;Brookhart etc.
People has also synthesized the nickel metal complex of cycloheptatriene ylidene ligands support;Peter W.Roesky and Siegfried Blechert
Et al. report calcium class, zinc class cycloheptatriene metal carbonyl complexes, and be catalyzed the hydrogen of the terminal olefine with amido substituent group with it
Aminating reaction, has very high activity;The cycloheptatriene Base Metal that Selvarajan Nagendran et al. report has synthesized germanium is joined
Compound, Nathan M.West research group successfully synthesizes the platinum metal complex of cycloheptatriene ylidene ligands support.To sum up institute
State, the catalyst that this part and part main group metal (such as Zn, Mg, Ca, Al etc.) and transition metal (Ni, Ti, Pt etc.) synthesize
Applied in organic molecule reaction and vinyl polymerization.But the syntheti c route of cycloheptatriene metal carbonyl complexes is relatively
For complexity, typically from cycloheptatriene ylidene ligands, react former to slough the hydrogen on cycloheptatriene part at -78 DEG C with KH
Son, adds metal halide reaction.This process reaction takes longer, and make that the method do not possess heavy industrialization process can
Can, therefore, those skilled in the art is highly desirable to be found more economy, environmental protection and is suitable for industrialized preparation cycloheptatriene base
The method of metallic compound.At present, cycloheptatriene base rare-earth metal catalyst, preparation method and its application in the polymerization
Not yet someone's report.
Content of the invention
An object of the present invention is to provide a kind of cycloheptatriene base rare-earth metal catalyst;The second object of the present invention
It is to provide a kind of preparation method of cycloheptatriene base rare-earth metal catalyst;The third object of the present invention is to provide a kind of ring
The application of heptantriene base rare-earth metal catalyst.
The purpose of the present invention is realized by technical scheme below:
A kind of cycloheptatriene base rare-earth metal catalyst, described cycloheptatriene base rare-earth metal catalyst structural formula have as
Lower I, II two kind:
Formula I, in II, R1、R2And R8It is the initiating group being connected with rare earth metal;L1And L2It is joining of being connected with rare earth metal
Position group;R4、R10And R10' it is substituted radical on cycloheptatriene skeleton N atom;R3、R9And R9' it is cycloheptatriene skeleton double bond
On substituted radical;R5、R6、R7、R11、R11’、R12、R12’、R13And R13' it is substituent group on cycloheptatriene ligand backbone;Ln1、
Ln2It is rare earth metal;
Wherein, R1、R2、R8All preferably alkyl, trimethyl silicon substrate, amido, imido grpup, alkoxyl, benzyl, cyclopentadienyl group,
Indenyl, fluorenyl and halogen one of F, Cl, Br or I;
L1、L2Preferably phosphide ligands (as triphenyl phosphorus), ethers part (as oxolane, ether), neutral amine ylidene ligands
One of (as pyridine), imidazoles, carbazole, oxazole, DMF;
R4Preferably 2,6- dimethyl benzene, 2,6- diisopropyl benzene, 2- tert-butyl benzene, 2- methyl-6-tert butyl benzene, 2,6- bis-
Phenyl benzene, phenyl-pentafluoride, 2,6- dibromobenzene, 3,5- trifluoromethylbenzene, 2- methylbenzene, 2- methyl -6- trifluoromethylbenzene, 2,6- difluoro
One of benzene;
R10Preferably one of isopropyl, the tert-butyl group, normal-butyl;
R3Preferably 2,6- dimethylaniline, 2,6- diisopropyl aniline, 2- tert-butyl group aniline, 2- methyl-6-tert butyl benzene
Amine, 2,6- diphenyl aniline, pentafluoroaniline, 2,6- dibromo aniline, 3,5- 5-trifluoromethylaniline, 2-aminotoluene, 2- methyl -6-
One of 5-trifluoromethylaniline, 2,6- difluoroaniline;
R9And R9' preferred one of oxygen atom, 2-aminopropane., tert-butylamine;
R5、R11And R11' preferably hydrogen atom, methyl, ethyl, alkoxyl, isopropyl, the tert-butyl group, normal-butyl, nitro, amino,
Atomic iodine, bromine atoms, phenyl, benzyl, itrile group, sulfur phenenyl, anilino-, phenylol, thiophenyl and 3,5- difluoromethane thiophenyl
One of;
R6、R7Preferably phenyl, benzyl, anthryl, naphthyl, phenanthryl, sulfur phenenyl, anilino-, phenylol, thiophenyl and 3,5- bis-
One of fluoromethane thiophenyl;
R12、R12’、R13And R13' preferably hydrogen atom, methyl, ethyl, isopropyl, the tert-butyl group, normal-butyl, alkoxyl, itrile group,
One of amino, atomic iodine, bromine atoms, nitro, itrile group;
Ln1、Ln2Preferably scandium (Sc), lutecium (Lu), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nb), promethium (Pm), samarium
(Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm) or ytterbium (Yb);
A kind of preparation method of cycloheptatriene base rare-earth metal catalyst, methods described step is as follows:
(1) cycloheptatriene ylidene ligands are prepared;
First, weigh tropolone, paratoluensulfonyl chloride in reactor, under room temperature, add good solvent, good solvent
Preferably dichloromethane, starts stirring mixture, then is added dropwise over triethylamine in mixture, now will produce yellow muddy
Material;Separately add good solvent diluting reaction;At room temperature under the atmosphere of nitrogen protection, after stir about 32h, obtain compound
a.The mol ratio of wherein tropolone, paratoluensulfonyl chloride and triethylamine is 1:1:1;
Secondly, at low temperature, amido substituent is slowly added dropwise in a;Mixture is stirred at room temperature overnight.With good molten
After agent and poor solvent carry out recrystallization, that is, obtain the product b containing double bond O;
Finally, by the CH of b product2Cl2Solution is slowly added to Et3OBF4In solution, certain time is stirred at room temperature
Afterwards, then amido substituent slowly it is added dropwise in above-mentioned reaction bulb, question response recovers to room temperature, is stirred overnight, is contained
There is the mixture c of target product;Add good solvent 25~35mL in mixture c, layering obtains aqueous phase and organic faciess, to organic
After adding solid drier 5~10g in phase, filter, be spin-dried for, obtain crude product.Obtained by the method for column chromatography purified product again
To described cycloheptatriene ylidene ligands;
(2) prepare cycloheptatriene base rare-earth metal catalyst;
First, reactor is placed in glove box, described for step (1) cycloheptatriene part is added dropwise to dissolved with metal
In the solution in source, stirring reaction 6h under room temperature, obtain mixture, described mixture is filtered, takes gained liquid to be concentrated, obtain
To cycloheptatriene base rare earth catalyst crude product, obtain cycloheptatriene base catalyzing of rare-earth metal by after described crude product recrystallization
Agent;
Wherein, reaction temperature is 20~25 DEG C, and cycloheptatriene ylidene ligands are 1 with the mol ratio of source metal:1 or 2:1;Step
(1) the preferred dichloromethane of good solvent in;Preferably anhydrous magnesium sulfate (MgSO4) described organic faciess are dried;Gold in step (2)
Genus source preferably two oxolane-three (trimethyl silicane methyl)-rare earth compound, molecular formula is [Ln (CH2SiMe3)3
(THF)2];
A kind of application of cycloheptatriene base rare-earth metal catalyst, described cycloheptatriene base rare-earth metal catalyst and alkyl
Aluminon and organic boron salt composition catalyst system and catalyzing, for catalyzed alkene, alkynes, the homopolymerization of polar monomer and copolymerization, or
Alkene, alkynes, polar monomer respectively with CO2Copolyreaction;
Wherein, the mol ratio of alkyllithium reagent, organic boron salt and cycloheptatriene base rare-earth metal catalyst is 2~100:1
~100:1;Alkyllithium reagent is molecular formula is AlR3Alkyl aluminum, molecular formula be HAlR2Alkyl-al hydride, molecular formula be
AlR2One of the alkyl aluminum chloride of Cl or aikyiaiurnirsoxan beta, R is alkyl;
The step of described homopolymerization is as follows:
Reaction bulb is placed in glove box, reaction bulb sequentially adds described cycloheptatriene base rare earth catalyst, 5~
10mL good solvent, alkyl aluminum, alkene, alkynes or polar monomer, organic boron salt, under agitation after reaction 0.3~6h, by reaction bulb
Take out, add chain terminating agent, make the stopping of reaction;Reactant liquor is poured into sedimentation in ethanol, separates out solid matter, by described solidss
Matter removes solvent to constant weight with vacuum drying oven at 30 DEG C, obtains homopolymerization products;
Wherein alkene, alkynes or polar monomer, alkyllithium reagent, organic boron salt is rubbed with cycloheptatriene base rare earth catalyst
That ratio is 200~600:2~100:1~100:1;Reaction temperature is 25~90 DEG C.
The step of described copolyreaction is as follows:
Reaction bulb is placed in glove box, reaction bulb sequentially adds described cycloheptatriene base rare earth catalyst, 1~
40mL good solvent, alkyl aluminum, reactant a or reactant b, organic boron salt, under agitation after reaction 3~24h, reaction bulb is taken
Go out, add chain terminating agent, make the stopping of reaction;Reactant liquor is poured into sedimentation in ethanol, separates out solid matter, by described solid matter
Remove solvent to constant weight at 30 DEG C with vacuum drying oven, obtain copolymerization product;
Wherein, reactant a or reactant b, alkyllithium reagent, organic boron salt and cycloheptatriene base rare earth catalyst mole
Than for 200~5000:2~100:1~100:1;Reaction temperature is 25~70 DEG C;Reactant a is branched-chain alkene, cycloolefins, alkynes
In hydrocarbon, polar monomer two kinds, reactant b is one of branched-chain alkene, cycloolefins, alkynes, polar monomer and CO2.
The preferred trimethyl aluminium of described alkyl aluminum, triethyl aluminum, tri-n-n-propyl aluminum, three n-butylaluminum, triisopropylaluminiuand, three different
Butyl aluminum, three hexyl aluminum, thricyclohexyl aluminum, trioctylaluminum, triphenyl aluminum, three p-methylphenyl aluminum, tribenzyl aluminum, ethyl dibenzyl
One of aluminum, ethyl di-p-tolyl aluminum and diethylbenzyl aluminum;
Described alkyl-al hydride preferably hydrogenates dimethyl aluminum, diethyl aluminium hydride, hydrogenation diη-propyl aluminum, hydrogenation two positive fourths
Base aluminum, hydrogenation diisopropyl aluminum, diisobutylaluminium hydride, hydrogenation diamyl aluminum, hydrogenation dihexyl aluminum, hydrogenation dicyclohexyl aluminum,
Hydrogenation dioctyl aluminum, hydrogenated diphenyl aluminum, hydrogenation di-p-tolyl aluminum, hydrogenation dibenzyl aluminum, ethyl hydride benzyl aluminum and hydrogenation
One of ethyl p-methylphenyl aluminum;
Described alkyl aluminum chloride is preferred:Chlorodimethylalumiu, diethylaluminum chloride, chlorination diη-propyl aluminum, chlorination two are just
Butyl aluminum, chlorination diisopropyl aluminum, di-isobutyl aluminum chloride, chlorination diamyl aluminum, chlorination dihexyl aluminum, chlorination dicyclohexyl
Aluminum, chlorination dioctyl aluminum, chlorinated diphenyl base aluminum, chlorination di-p-tolyl aluminum, chlorination dibenzyl aluminum, tonsilon benzyl aluminum and chlorine
Change one of ethyl p-methylphenyl aluminum;
Described aikyiaiurnirsoxan beta is preferred:In MAO, ethylaluminoxane, n-pro-pyl aikyiaiurnirsoxan beta and normal-butyl aikyiaiurnirsoxan beta one
Kind;
The described preferred triphenyl of organic boron salt (methyl)-four (phenyl-pentafluoride) boron salt ([Ph3C][B(C6F5)4]), phenyl-
Dimethylamino-four (phenyl-pentafluoride) boron salt ([PhMe2NH][B(C6F5)4]), phenyl-dimethyl amino-tetraphenyl boron salt
([PhMe2NH][BPh4]) or three (phenyl-pentafluoride) boron salt (B (C6F5)3One of);
Described branched-chain alkene optimal ethylene, propylene, 1-butylene, 1- amylene, 4-methyl-1-pentene, 1- hexene, 1- heptene,
1- octene, 1-decene, 1- dodecylene, tetradecene, cetene, 1- eicosylene, styrene, Alpha-Methyl benzene second
Alkene, 3- 1-chloro-4-methyl-benzene, 1,3- butadiene, isoprene, 1,3- cyclohexadiene, 1,5- pentadiene, 1,6- hexadiene and two
One of vinyl benzene;
The preferred norborene of described cycloolefins, polarity norborene, norbornadiene, ethylidene norbornene, phenyl fall
One of bornylene, vinyl norbornene and dicyclopentadiene;
The preferred acetylene of described alkynes, phenylacetylene, to one of phenylacetylene and diacetylene aromatic hydrocarbons;
Described polar monomer is divided into epoxyalkane and lactone, wherein epoxyalkane optimization ethylene oxide, expoxy propane, 1,
2- epoxy butane, 2,3- epoxy butane, different epoxy butane, epoxychloropropane, epoxy bromopropane, methyl glycidyl ether, allyl
Base glycidyl ether, butyl glycidyl ether, 2- ethyl hexylen glycidyl ether, trifluoro-epoxy propane, lactone be ε-oneself in
One of ester, beta-butyrolactone, δ-valerolactone, lactide, Acetic acid, hydroxy-, bimol. cyclic ester and 3- methyl-Acetic acid, hydroxy-, bimol. cyclic ester;
Described chain terminating agent preferably contains the ethanol of 5%2,6- di-tert-butyl-4-methy phenol, and the volume with ethanol is
100% meter, wherein, volume ratio shared by 2,6- di-tert-butyl-4-methy phenols is 5%;The preferred toluene of good solvent.
Beneficial effect
(1) cycloheptatriene base rare-earth metal catalyst of the present invention, is with tropolone as initial feed, former
Material is cheap and easy to get, and is easy to modify;
(2) preparation method of cycloheptatriene base rare-earth metal catalyst of the present invention, business efficiency is high, the feature of environmental protection
Good, suitable industrialized production;
(3) cycloheptatriene base rare-earth metal catalyst of the present invention, alkyllithium reagent and organic boron salt form
Catalyst system and catalyzing, can carry out branched-chain alkene, cycloolefins, alkynes, the homopolymerization of polar monomer and copolyreaction or branched-chain alkene, cyclenes
Hydrocarbon, alkynes, polar monomer and CO2Copolyreaction, obtain a series of new polymeric materials with ad hoc structure;
(4) cycloheptatriene base rare-earth metal catalyst of the present invention, in catalysis L- lactide and 6-caprolactone polymerization
When, the yield of the homopolymerization of 6-caprolactone can be made to reach 74.9%, to the yield of the homopolymerization of L- lactide up to 100%.
(5) cycloheptatriene base rare-earth metal catalyst of the present invention, when being catalyzed isoprene polymerization, yield is permissible
Reach 100%, the selectivity along Isosorbide-5-Nitrae-structure reaches as high as 94.34%.This is a kind of new isoprene rubber of not yet report
Glue material, the research further to its physicochemical property will may consequently contribute to find suitable application purpose for it.
Brief description
Fig. 1 is the crystal structure figure of the X-ray single crystal diffraction sign of cycloheptatriene base scandium catalyst.
Specific embodiment
The present invention will be further described with specific embodiment below in conjunction with the accompanying drawings, but not limited to this.
The main agents information mentioned in following examples is shown in Table 1;Key instrument and facility information are shown in Table 2.
Table 1
Table 2
In following examples, polymerization activity is by formula Activity=(m yeild)/(ncatTime) calculate.Its
In, Activity is living polymerization, and unit is kg mol-1·h-1, m be branched-chain alkene, cycloolefins, alkynes, polar monomer or
CO2Quality, yield be yield, ncatFor the amount of catalyst material, time is the time used by polymerization.
Polyisoprene microstructure can be by1H-NMR and13C-NMR spectrogram is given, and selectivity specific formula for calculation is such as
Under:
(1) selectivity (proportion) of 1,4- polyisoprene:
Mol 1,4-IP%={ IH1/(IH1+0.5IH2)}×100
(2) selectivity (proportion) of 3,4- polyisoprene:
Mol 3,4-IP%={ 0.5IH2/(IH1+0.5IH2)}×100
(3) along the selectivity (proportion) of 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%={ IC3/(IC1+IC2+IC3)}×100
(5) selectivity (proportion) of 3,4- polyisoprene:
Mol 3,4-IP%={ IC2/(IC1+IC2+IC3)}×100
Wherein, IP is polyisoprene, IH1For1Integration at 5.13ppm in H spectrum;IH2For1Long-pending at 4.72ppm in H spectrum
Point;IC1For13Integration at 23.2ppm in C spectrum;IC2For13Integration at 18.5ppm in C spectrum;IC3For13At 15.9ppm in C spectrum
Integration.
Embodiment 1
(1) cycloheptatriene ylidene ligands are prepared
First, weigh tropolone 5.3g (43mmol) and paratoluensulfonyl chloride 8.2g (43mmol) and arrive reactor
In, add 60mL dichloromethane under room temperature, start stirring mixture, then be added dropwise over 6mL (43mmol) three second in mixture
Amine, now will produce yellow muddy material.Separately add 60mL dichloromethane.At room temperature in the atmosphere of nitrogen protection
Under, after stir about 32h, obtain compound a.
Secondly, at low temperature, 2-aminopropane. (60mL) is slowly added dropwise in a (10.92g, 40.0mmol).Mixture is in room
After being stirred overnight under temperature, vacuum rotary steam, the material obtaining 2mol/L NaOH (60mL) and CH2Cl2(120mL) dissolve, layering,
Isolate organic faciess.Aqueous phase uses CH again2Cl2(120mL) extract 2 times.Merge organic faciess, washed with 20mL strong brine, and with anhydrous
MgSO4It is dried, sucking filtration, filtrate is spin-dried for, the solid CH obtaining2Cl2Carry out, after recrystallization, obtaining yellow solid b with normal hexane,
It is cycloheptatriene ylidene ligands, yield is 80.9%.
(2) prepare cycloheptatriene base scandium catalyst
First, reactor is placed in glove box, cycloheptatriene part prepared by step (1) (665.9mg,
4.08mmol) it is added dropwise to dissolved with Sc (CH2SiMe3)3(thf)2In the toluene solution of (920mg, 2.04mmol), in stirring
Lower reaction 6h, obtains mixture c;Wherein, reaction temperature is 25 DEG C;
Secondly, described mixture c is filtered, take gained liquid to be concentrated, obtain cycloheptatriene base scandium catalyst and slightly produce
Product, will obtain yellow powder 0.720g, as cycloheptatriene base scandium catalyst d after described crude product recrystallization, yield is 65%.
It is the crystal structure figure that the X-ray single crystal diffraction of cycloheptatriene base scandium catalyst d characterizes as shown in drawings.
Example 5 below~embodiment 11 and embodiment 16~embodiment 18 are the cycloheptatriene base described in embodiment 1
The application of scandium catalyst d.
Embodiment 2
(1) cycloheptatriene ylidene ligands are prepared
First, weigh tropolone 5.3g (43mmol) and paratoluensulfonyl chloride 8.2g (43mmol) and arrive reactor
In, add 60mL dichloromethane under room temperature, then be added dropwise over 4.4g (6mL, 43mmol) triethylamine in mixture, separately add
60mL dichloromethane.Under room temperature under nitrogen protection, after stir about 32h, obtain compound a.The operation of compound b is with embodiment 1.
Secondly, by the CH of b product (1.37g, 9.20mmol)2Cl2Solution is slowly added to Et3OBF4(1.75g, 9.21mmol) is molten
In liquid, after 3h is stirred at room temperature, put plate, until when new product point no longer changes, reaction is cooled to 0 DEG C, then different
Propylamine (20mL) is added dropwise in above-mentioned reaction bulb slowly, and question response recovers to room temperature, is stirred overnight, and obtains producing containing target
The Mischung of thing.Oily mater after vacuum rotary steam NaOH (10mL) and CH2Cl2(20mL) dissolve, separate organic faciess.Aqueous phase
Use CH2Cl2(20mL) extract 2 times.Merge organic faciess, washed with 20mL strong brine, and use anhydrous MgSO4It is dried.Sucking filtration, is spin-dried for.
Obtain crude product.Again cycloheptatriene ylidene ligands f described in 1.39g are obtained by the method for column chromatography purified product, yield is
47.9%.
(2) prepare cycloheptatriene base scandium catalyst
First, reactor is placed in glove box, cycloheptatriene ylidene ligands f prepared by step (1) (613.0mg,
3mmol) it is added dropwise to dissolved with Sc (CH2SiMe3)3(thf)2In the toluene solution of (676.2mg, 1.5mmol), under agitation
Reaction 6h, obtains mixture g;Wherein, reaction temperature is 25 DEG C;
Secondly, after described mixture g being filtered, concentrated, obtained cycloheptatriene base scandium catalyst crude product, will be described
Yellow powder 0.530g, as cycloheptatriene base scandium catalyst h is obtained, yield is 58% after crude product recrystallization.
Example 1 below 2~15 is the aggregated application of the cycloheptatriene base scandium catalyst h described in embodiment 2.
Embodiment 3
(1) cycloheptatriene ylidene ligands are prepared
Compound a, the operation of b are with embodiment 1.Afterwards, by the CH of b product (1.37g, 9.20mmol)2Cl2Solution is slowly
It is added to Et3OBF4In (1.75g, 9.21mmol) solution, after 3h is stirred at room temperature, put plate, determining has new product to give birth to
Becoming, until when new product point no longer changes, reaction is cooled to 0 DEG C, then 2-aminopropane. (20mL) being delayed with the speed that 1s/ drips
Slow is added dropwise in above-mentioned reaction bulb, and question response recovers to room temperature, is stirred overnight, and obtains the Mischung containing target product.
Again cycloheptatriene ylidene ligands f described in 1.39g are obtained by the method for column chromatography purified product, yield is 47.9%.
(2) prepare cycloheptatriene base lutecium catalyst
First, reactor is placed in glove box, cycloheptatriene ylidene ligands f prepared by step (1) (326.9mg,
3.0mmol) it is added dropwise to dissolved with Lu (CH2SiMe3)3(thf)2In the toluene solution of (676.2mg, 1.5mmol), in stirring
Lower reaction 6h, obtains mixture i;Wherein, reaction temperature is 25 DEG C;
Secondly, after described mixture i being filtered, concentrated, obtained cycloheptatriene base lutecium catalyst crude product, will be described
Crude product obtains the cycloheptatriene base lutecium catalyst j of 0.699g after recrystallization at -33 DEG C, yield is 63%.
Embodiment 4
(1) cycloheptatriene ylidene ligands are prepared
The operation of compound a is with embodiment 1.Afterwards, at 0 DEG C, by 2-aminopropane. (60mL) be slowly added dropwise into a (10.92g,
40.0mmol) in.Mixture is stirred at room temperature overnight.The solid CH that post processing obtains2Cl2Carry out recrystallization with normal hexane
Afterwards, obtain yellow solid b.Finally, by the CH of b product (1.37g, 9.20mmol)2Cl2Solution is slowly added to Et3OBF4
In (1.75g, 9.21mmol) solution, after 3h is stirred at room temperature, put plate, when determination has new product to generate, will reaction cooling
To 0 DEG C, then 2-aminopropane. (20mL) is added dropwise in above-mentioned reaction bulb slowly, question response recovers to room temperature, is stirred overnight, obtains
Arrive the Mischung containing target product.Again cycloheptatriene ylidene ligands described in 1.39g are obtained by the method for column chromatography purified product
F, yield is 47.9%.
(2) prepare cycloheptatriene base yttrium catalyst
First, reactor is placed in glove box, cycloheptatriene ylidene ligands f prepared by step (1) (1175.2mg,
4.7mmol) it is added dropwise to dissolved with Y (CH2SiMe3)3(thf)2In the toluene solution of (1162.8mg, 2.4mmol), in stirring
Lower reaction 6h, obtains mixture k;Wherein, reaction temperature is 25 DEG C;
Secondly, after described mixture k being filtered, concentrated, obtained cycloheptatriene base lutecium catalyst crude product, will be described
Crude product obtains the cycloheptatriene base lutecium catalyst l of 0.989g after recrystallization at -33 DEG C, yield is 63%.
Embodiment 5
Reactor is placed in glove box, sequentially adds 20 μm of ol cycloheptatriene base scandium catalyst d, 40 μm of ol in eggplant bottle
'siPrOH, adds 2mL THF, after 10~30min is stirred at room temperature, the THF solution of 3mL L- containing 8mmol lactide adds
In catalyst mixture, stirring reaction 2.5h, 25 DEG C of reaction temperature, after solution becomes sticky, add volume fraction 10%
The ethanol solution stopped reaction of HCl, then pour sedimentation in ethanol into, filter, washing obtains white polymer, by described solid matter
It is vacuum dried at 30 DEG C, remove solvent to constant weight, obtain polylactide, net weight 0.055g, conversion ratio 5.8%, polymerization activity
For 1.64kg mol-1·h-1;Number-average molecular weight M of gpc analysis polylactiden=23 × 104, molecular weight distribution Mw/Mn=
1.58.
Embodiment 6
Reactor is placed in glove box, sequentially adds 20 μm of ol cycloheptatriene base scandium catalyst d, 40 μm of ol in eggplant bottle
EtONa, add 2mL CH2Cl2, after 10~30min is stirred at room temperature, by the CH of 3mL L- containing 8mmol lactide2Cl2Solution,
Add in catalyst mixture, stirring reaction 2.5h, 25 DEG C of reaction temperature, remaining operation, with embodiment 5, obtains poly- third friendship
Ester, net weight 1.179g, conversion ratio is 100%, and polymerization activity is 23.58kg mol-1·h-1;The number of gpc analysis polylactide
Average molecular weight Mn=15 × 104, molecular weight distribution Mw/Mn=1.31.
Embodiment 7
Reactor is placed in glove box, sequentially adds 20 μm of ol cycloheptatriene base scandium catalyst d, 40 μm of ol in eggplant bottle
EtONa, add 2mL THF, stirring 10~30min after, by 3mL contain 8mmol 6-caprolactone THF solution, add catalysis
In agent composition, stirring reaction 2.5h, remaining operation, with embodiment 5, obtains polycaprolactone 0.683g, and conversion ratio is 74.9%,
Polymerization activity is 13.68kg mol-1·h-1;Number-average molecular weight M of gpc analysis polycaprolactonen=9 × 104, molecular weight distribution
Mw/Mn=1.69.
Embodiment 8
Reactor is placed in glove box, sequentially adds 20 μm of ol cycloheptatriene base scandium catalyst d, 40 μm of ol in eggplant bottle
EtONa, add 2mL CH2Cl2, after stirring 10~30min, by 3mL contain the ε of the L- lactide of 4mmol and 4mmol-oneself in
The CH of ester2Cl2Solution, adds in catalyst mixture, stirring reaction 4h, and remaining operation, with embodiment 5, obtains L- lactide
With the copolymer of 6-caprolactone, net weight 0.859g, polymerization activity is 34.36kg mol-1·h-1;The number of gpc analysis copolymer
Average molecular weight Mn=8 × 104, molecular weight distribution Mw/Mn=1.33.
Embodiment 9
Reactor is placed in glove box, sequentially adds 25 μm of ol cycloheptatriene base scandium catalyst d, 5mL first in eggplant bottle
Benzene, 50 μm of ol AliBu3, 5mmol phenylacetylene and 25 μm of ol [PhNHMe2][B(C6F5)4], by eggplant after reaction 0.3h at 50 DEG C
Bottle takes out, and adds 30mL to contain the ethanol of 5%2,6- di-tert-butyl-4-methy phenol, makes the stopping of reaction;Reactant liquor ethanol is entered
Row sedimentation, separates out white solid matter, described solid matter is vacuum dried at 30 DEG C, removes solvent to constant weight, is gathered
Phenylacetylene, net weight 0.29g, conversion ratio 57%;Number-average molecular weight M of gpc analysis polyphenylacetylenen=2 × 104, molecular weight distribution
Mw/Mn=1.73.
Embodiment 10
Reactor is placed in glove box, sequentially adds 25 μm of ol cycloheptatriene scandium catalyst d in eggplant bottle, 5mL toluene,
50μmol AlMe3, 5mmol expoxy propane and 25 μm of ol [Ph3C][B(C6F5)4], response time 5h, 50 DEG C of reaction temperature, remaining
Operation, with embodiment 9, obtains poly(propylene oxide), net weight 0.26g, conversion ratio 90%;The equal molecule of number of gpc analysis poly(propylene oxide)
Amount Mn=17 × 104, molecular weight distribution Mw/Mn=1.62.
Embodiment 11
Reactor is placed in glove box, sequentially adds 21 μm of ol cycloheptatriene base scandium catalyst d, 25mL first in eggplant bottle
Benzene, 42 μm of ol AliBu3, 53mmol norborene, 53mmol Isosorbide-5-Nitrae-butadiene, and 21 μm of ol [Ph3C][B(C6F5)4], reaction
Time 3h, 25 DEG C of reaction temperature, remaining operation, with embodiment 9, obtains the copolymer of norborene and Isosorbide-5-Nitrae-butadiene, conversion ratio
79%;Number-average molecular weight M of gpc analysis copolymern=3.5 × 104, molecular weight distribution Mw/Mn=1.69.
Embodiment 12
Reactor is placed in glove box, sequentially adds 25 μm of ol cycloheptatriene base scandium catalyst h, 5mL first in eggplant bottle
Benzene, 50 μm of ol AliBu3, 15mmol isoprene and 25 μm of ol [Ph3C][B(C6F5)4], the response time is 6h, reaction temperature 25
DEG C, remaining operation, with embodiment 9, obtains polyisoprene, net weight 0.714g, conversion ratio 70%, polymerization activity is 4.8kg
mol-1·h-1;The number-average molecular weight of gpc analysis polyisoprene is Mn=10 × 103, molecular weight distribution Mw/Mn=1.54;Suitable
1,4- polymerization selectivity is 84%.
Embodiment 13
Reactor is placed in glove box, sequentially adds 25 μm of ol cycloheptatriene base scandium catalyst h, 5mL first in eggplant bottle
Benzene, 50 μm of ol AliBu3, 5mmol isoprene and 25 μm of ol [Ph3C][B(C6F5)4], the response time is 6h, reaction temperature 25
DEG C, remaining operation, with embodiment 9, obtains polyisoprene, net weight 0.335g, conversion ratio 98.5%, polymerization activity is 2.2kg
mol-1·h-1;The number-average molecular weight of gpc analysis polyisoprene is Mn=15 × 103, molecular weight distribution Mw/Mn=1.76;Suitable
1,4- polymerization selectivity is 94.34%.
Embodiment 14
Reactor is placed in glove box, sequentially adds 25 μm of ol cycloheptatriene base scandium catalyst h, 10mL first in eggplant bottle
Benzene, 2.5mmol AliBu3, 5mmol isoprene and 2.5mmol [PhNHMe2][B(C6F5)4], response time 3h, reaction temperature
25 DEG C, remaining operation, with embodiment 9, obtains polyisoprene, net weight 0.306g, conversion ratio 90%, polymerization activity is 4.1kg
mol-1·h-1;The number-average molecular weight of gpc analysis polyisoprene is Mn=18 × 103, molecular weight distribution Mw/Mn=1.98;Suitable
1,4- is polymerized selectivity 89%.
Embodiment 15
Reactor is placed in glove box, sequentially adds 25 μm of ol cycloheptatriene base scandium catalyst h, 10mL first in eggplant bottle
Benzene, 2.5mmol AliBu3, 5mmol isoprene and 2.5mmol [PhNHMe2][B(C6F5)4], response time 3h, reaction temperature
90 DEG C, remaining operation, with embodiment 9, obtains polyisoprene, net weight 0.34g, conversion ratio 100%, polymerization activity is 4.5kg
mol-1·h-1;The number-average molecular weight of gpc analysis polyisoprene is Mn=12 × 103, molecular weight distribution Mw/Mn=2.27;Suitable
1,4- is polymerized selectivity 76%.
Embodiment 16
Reactor is placed in glove box, weighs 2g norbornene monomer with the clean bottle of 20mL and be put in 50mL eggplant bottle
In, add 4.57mL toluene, add 0.5 μm of ol cycloheptatriene base scandium catalyst d, Deca AlMe with syringe3Toluene solution 8 μ
L.After 1h, take out glove box acidic ethanol (ethanol:Concentrated hydrochloric acid=20:1) 30mL degradation reaction liquid, filters, and is washed with ethanol
Wash and leach solid;Solid is tried one's best after pulverizing, 30 DEG C of vacuum drying of vacuum drying oven, remove solvent to constant weight, obtain poly- norborneol
Alkene 0.04g, yield 2.0%, polymerization activity is 40.0kg mol-1·h-1;The number-average molecular weight of gpc analysis polynorbornene is
Mn=15 × 103, molecular weight distribution Mw/Mn=1.27.
Embodiment 17
Reactor is placed in glove box, sequentially adds 25 μm of ol cycloheptatriene base scandium catalyst d, 5mL first in eggplant bottle
Benzene, 250 μm of ol AliBu3, 10mmol styrene and 25 μm of ol [Ph3C][B(C6F5)4], the response time is 4h, reaction temperature 25
℃.Remaining operation, with embodiment 9, obtains polystyrene;Net weight 0.382g, conversion ratio 36.7%, polymerization activity is 3.82kg
mol-1·h-1;The number-average molecular weight of gpc analysis polystyrene is Mn=90 × 103, molecular weight distribution Mw/Mn=1.49.
Embodiment 18
Reactor is placed in glove box, sequentially adds 50 μm of ol cycloheptatriene base scandium catalyst d, 1mL first in eggplant bottle
Benzene, 20mol expoxy propane, seal reactor, be transferred out of glove box, in reactor, be passed through CO2, regulation pressure to 6Mpa, so
Post-heating, to 70 DEG C, reacts 24h, is subsequently cooled to room temperature, with chloroform dissolving, adds methanol to obtain white solid, is washed with methanol,
Vacuum drying, obtain expoxy propane and CO2Copolymer;Yield is 43.0%, and molecular weight is Mn=31 × 103, molecular weight distribution
Mw/Mn=1.40.
The present invention includes but is not limited to above example, and carry out under every principle in spirit of the present invention 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 cycloheptatriene base rare-earth metal catalyst it is characterised in that:Described cycloheptatriene base rare-earth metal catalyst knot
Structure formula has following I, II two kind:
Wherein, R1、R2And R8It is the initiating group being connected with rare earth metal;L1And L2It is the coordinating group being connected with rare earth metal;
R4、R10And R10' it is substituted radical on the N atom being connected with cycloheptatriene base backbone carbon atoms;R3、R9And R9' be and cycloheptyl three
The substituted radical that thiazolinyl backbone carbon atoms are connected;R5、R6、R7、R11、R11’、R12、R12’、R13And R13' it is cycloheptatriene part bone
Substituent group on frame;Ln1、Ln2It is rare earth metal;
R1、R2、R8Be alkyl, trimethyl silicon substrate, amido, imido grpup, alkoxyl, benzyl, cyclopentadienyl group, indenyl, fluorenyl and
Halogen one of F, Cl, Br or I;
L1, L2 are ethers part, neutral amine ylidene ligands, and wherein, described ethers part is one of oxolane, ether;
Described neutral amine ylidene ligands are one of pyridine, imidazoles, carbazole, oxazole, DMF;
R4For 2,6- 3,5-dimethylphenyl, 2,6- diisopropyl phenyl, 2- tert-butyl-phenyl, 2- methyl-6-tert butyl phenyl, 2,6-
Diphenyl phenyl, pentafluorophenyl group, 2,6- dibromo phenyl, 3,5- trifluoromethyl, 2- aminomethyl phenyl, 2- methyl -6- fluoroform
One of base phenyl, 2,6- difluorophenyl;
R10For one of isopropyl, the tert-butyl group, normal-butyl;
R3For 2,6- accelerine base, 2,6- diisopropyl benzene amido, 2- tertiary-butyl anilino, 2- methyl-6-tert butyl aniline
Base, 2,6- diphenyl benzene amido, phenyl-pentafluoride amido, 2,6- dibromobenzene amido, 3,5- trifluoromethylbenzene amido, 2-aminotoluene
One of base, 2- methyl -6- trifluoromethylbenzene amido, 2,6- difluoroaniline;
R9And R9' it is one of oxygen atom, isopropylamine base, tert-butylamine base;Wherein, R9And R9' identical;
R5、R11And R11' to be hydrogen atom, methyl, ethyl, alkoxyl, isopropyl, the tert-butyl group, normal-butyl, nitro, amino, iodine former
In son, bromine atoms, phenyl, benzyl, itrile group, sulfur phenenyl, anilino-, phenylol, thiophenyl and 3,5- difluoromethane thiophenyl
A kind of;Wherein, R11And R11' identical;
R6、R7It is phenyl, benzyl, anthryl, naphthyl, phenanthryl, sulfur phenenyl, anilino-, phenylol, thiophenyl and 3,5- difluoro first
One of alkane thiophenyl;
R12、R12’、R13And R13' it is hydrogen atom, methyl, ethyl, isopropyl, the tert-butyl group, normal-butyl, alkoxyl, itrile group, ammonia
One of base, atomic iodine, bromine atoms, nitro, itrile group;Wherein, R12And R12' identical, R13And R13' identical;
Ln1、Ln2Be scandium (Sc), lutecium (Lu), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nb), promethium (Pm), samarium (Sm),
Europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm) or ytterbium (Yb).
2. a kind of preparation method of cycloheptatriene base rare-earth metal catalyst structure formula II as claimed in claim 1, its feature
It is:Methods described step and condition are as follows:
(1) cycloheptatriene ylidene ligands are synthesized:
First, weigh tropolone, paratoluensulfonyl chloride in reactor, add good solvent dichloromethane under room temperature, open
Beginning stirring mixture, then it is added dropwise over triethylamine in mixture, now will produce yellow muddy material, separately add good
Solvent dilution reacts;At room temperature under the atmosphere of nitrogen protection, after stir about 32h, obtain compound a;Wherein cycloheptatriene
The mol ratio of phenolic ketone, paratoluensulfonyl chloride and triethylamine is 1:1:1;
Secondly, at low temperature, amido substituent is slowly added dropwise in a, mixture is stirred at room temperature overnight, with good solvent and
After poor solvent carries out recrystallization, that is, obtain the product b containing double bond O;
Finally, by the CH of b product2Cl2Solution is slowly added to Et3OBF4In solution, after certain time is stirred at room temperature, then
Amido substituent is added dropwise in said mixture slowly, question response recovers to room temperature, is stirred overnight, obtains containing target
The mixture c of product;Add good solvent 25~35mL in mixture c, layering obtains aqueous phase and organic faciess, adds in organic faciess
After entering solid drier 5~10g, filter, be spin-dried for, obtain crude product, then obtained by the method for column chromatography purified product described
Cycloheptatriene ylidene ligands;
(2) prepare cycloheptatriene base rare-earth metal catalyst:
First, reactor is placed in glove box, described for step (1) cycloheptatriene part is added dropwise to dissolved with rare earth metal
In the solution in source, stirring reaction 6h under room temperature, obtain mixture, described mixture is filtered, takes gained liquid to be concentrated, obtain
To cycloheptatriene base rare earth catalyst crude product, obtain cycloheptatriene base catalyzing of rare-earth metal by after described crude product recrystallization
Agent.
3. cycloheptatriene base rare-earth metal catalyst as claimed in claim 2 preparation method it is characterised in that:Step (1)
Middle solid drier is anhydrous magnesium sulfate;In step (2), source metal is two oxolane-three (trimethyl silicane methyl)-rare earth gold
Belong to compound, molecular formula is [Ln (CH2SiMe3)3(THF)2], described Ln be scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium,
One of terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutecium;Me is methyl;THF is oxolane.
4. the cycloheptatriene base rare-earth metal catalyst described in a kind of claim 1 application it is characterised in that:Described cycloheptyl three
Thiazolinyl rare-earth metal catalyst forms catalyst system and catalyzing with alkyllithium reagent and organic boron salt, for catalyzed alkene, cycloolefins, alkynes
Hydrocarbon, the homopolymerization of polar monomer and copolymerization, or alkene, cycloolefins, alkynes, polar monomer respectively with CO2Copolyreaction;
Wherein, the mol ratio of alkyllithium reagent, organic boron salt and cycloheptatriene base rare-earth metal catalyst is 2~100: 1~100
∶1;Alkyllithium reagent is molecular formula is AlR3Alkyl aluminum, molecular formula be HAlR2Alkyl-al hydride, molecular formula be AlR2Cl's
One of alkyl aluminum chloride or aikyiaiurnirsoxan beta, R is alkyl.
5. a kind of cycloheptatriene base rare-earth metal catalyst according to claim 4 application it is characterised in that:Described equal
The step of poly- reaction is as follows:
Reaction bulb is placed in glove box, reaction bulb sequentially adds described cycloheptatriene base rare earth catalyst, 5~10mL is good
Solvent, alkyl aluminum, alkene, alkynes or polar monomer, organic boron salt, under agitation after reaction 0.3~6h, reaction bulb is taken out,
Add chain terminating agent, make the stopping of reaction;Reactant liquor is poured into sedimentation in ethanol, separates out solid matter, described solid matter is existed
Remove solvent to constant weight with vacuum drying oven at 30 DEG C, obtain homopolymerization products;
The mol ratio of wherein alkene, alkynes or polar monomer, alkyllithium reagent, organic boron salt and cycloheptatriene base rare earth catalyst
For 200~600:2~100:1~100:1;Reaction temperature is 25~90 DEG C.
6. a kind of cycloheptatriene base rare-earth metal catalyst according to claim 4 application it is characterised in that:Described common
The step of poly- reaction is as follows:
Reaction bulb is placed in glove box, reaction bulb sequentially adds described cycloheptatriene base rare earth catalyst, 1~40mL is good
Solvent, alkyl aluminum, reactant a or reactant b, organic boron salt, under agitation after reaction 3~24h, reaction bulb is taken out, adds
Chain terminating agent, makes the stopping of reaction;Reactant liquor is poured into sedimentation in ethanol, separates out solid matter, by described solid matter at 30 DEG C
Lower vacuum drying oven removes solvent to constant weight, obtains copolymerization product;
Wherein, reactant a or reactant b, alkyllithium reagent, organic boron salt with the mol ratio of cycloheptatriene base rare earth catalyst is
200~5000:2~100:1~100:1;Reaction temperature is 25~70 DEG C;Reactant a is branched-chain alkene, cycloolefins, alkynes, pole
Property monomer in two kinds, reactant b be one of branched-chain alkene, cycloolefins, alkynes, polar monomer and CO2.
7. cycloheptatriene base rare-earth metal catalyst according to claim 4 application it is characterised in that:
Described alkyl aluminum is trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, three n-butylaluminum, triisopropylaluminiuand, triisobutyl
Aluminum, three hexyl aluminum, thricyclohexyl aluminum, trioctylaluminum, triphenyl aluminum, three p-methylphenyl aluminum, tribenzyl aluminum, three n-butylaluminum,
One of ethyl di-p-tolyl aluminum and diethylbenzyl aluminum;
Described alkyl-al hydride be hydrogenation dimethyl aluminum, diethyl aluminium hydride, hydrogenation diη-propyl aluminum, hydrogenation di-n-butyl aluminum,
Hydrogenation diisopropyl aluminum, diisobutylaluminium hydride, hydrogenation diamyl aluminum, hydrogenation dihexyl aluminum, hydrogenation dicyclohexyl aluminum, hydrogenation two
Octyl group aluminum, hydrogenated diphenyl aluminum, hydrogenation di-p-tolyl aluminum, hydrogenation dibenzyl aluminum, ethyl hydride benzyl aluminum and ethyl hydride pair
One of tolyl aluminum;
Described alkyl aluminum chloride is:Chlorodimethylalumiu, diethylaluminum chloride, chlorination diη-propyl aluminum, chlorination di-n-butyl aluminum,
Chlorination diisopropyl aluminum, di-isobutyl aluminum chloride, chlorination diamyl aluminum, chlorination dihexyl aluminum, chlorination dicyclohexyl aluminum, chlorination two
Octyl group aluminum, chlorinated diphenyl base aluminum, chlorination di-p-tolyl aluminum, chlorination dibenzyl aluminum, tonsilon benzyl aluminum and tonsilon pair
One of tolyl aluminum;
Described aikyiaiurnirsoxan beta is:One of MAO, ethylaluminoxane, n-pro-pyl aikyiaiurnirsoxan beta and normal-butyl aikyiaiurnirsoxan beta;
Described organic boron salt is triphenyl (methyl)-four (phenyl-pentafluoride) boron salt ([Ph3C][B(C6F5)4]), phenyl-dimethyl ammonia
Base-four (phenyl-pentafluoride) boron salt ([PhMe2NH][B(C6F5)4]), three (phenyl-pentafluoride) boron salt (B (C6F5)3One of);
Described alkene is ethylene, propylene, 1-butylene, 1- amylene, 4-methyl-1-pentene, 1- hexene, 1- heptene, 1- octene, the 1- last of the ten Heavenly stems
Alkene, 1- dodecylene, tetradecene, cetene, 1- eicosylene, styrene, α-methyl styrene, 3- chloromethylbenzene
In ethylene, 1,3- butadiene, isoprene, 1,3- cyclohexadiene, 1,5- pentadiene, 1,6- hexadiene and divinylbenzene one
Kind;
Described cycloolefins be norborene, polarity norborene, norbornadiene, ethylidene norbornene, phenyl norbornene,
One of vinyl norbornene and dicyclopentadiene;
Described alkynes be acetylene, phenylacetylene, to one of phenylacetylene and diacetylene aromatic hydrocarbons;
Described polar monomer is divided into epoxyalkane and lactone, and wherein epoxyalkane is oxirane, expoxy propane, 1,2- epoxy
Butane, 2,3- epoxy butane, different epoxy butane, epoxychloropropane, epoxy bromopropane, methyl glycidyl ether, allyl glycidyl
Glycerin ether, butyl glycidyl ether, 2- ethyl hexylen glycidyl ether, trifluoro-epoxy propane, lactone is 6-caprolactone, β-fourth
One of lactone, δ-valerolactone, lactide, Acetic acid, hydroxy-, bimol. cyclic ester and 3- methyl-Acetic acid, hydroxy-, bimol. cyclic ester.
8. a kind of cycloheptatriene base rare-earth metal catalyst according to claim 5 or 6 application it is characterised in that:Institute
State the ethanol that chain terminating agent is containing 2,6- di-tert-butyl-4-methy phenol, counted for 100% with the volume of ethanol, wherein, 2,6- bis-
Volume ratio shared by tert-butyl-4-methyl-Phenol is 5%;Good solvent is toluene.
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