CN104592425A - Cycloheptatriene-base rare-earth metal catalyst, and preparation method and application thereof - Google Patents
Cycloheptatriene-base rare-earth metal catalyst, and preparation method and application thereof Download PDFInfo
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- CN104592425A CN104592425A CN201510059201.3A CN201510059201A CN104592425A CN 104592425 A CN104592425 A CN 104592425A CN 201510059201 A CN201510059201 A CN 201510059201A CN 104592425 A CN104592425 A CN 104592425A
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- AELLFKPPLQHPRV-UHFFFAOYSA-N CC(C)NC1=CC=CC=C/C1=N/C(C)C Chemical compound CC(C)NC1=CC=CC=C/C1=N/C(C)C AELLFKPPLQHPRV-UHFFFAOYSA-N 0.000 description 1
- FMWYXCHZBRHNKN-UHFFFAOYSA-N CC(C)NC1=CC=CC=CC1=O Chemical compound CC(C)NC1=CC=CC=CC1=O FMWYXCHZBRHNKN-UHFFFAOYSA-N 0.000 description 1
- MQSUJJCTCOKCCG-ACCUITESSA-N CCOC1=CC=CC=C/C1=N\C(C)C Chemical compound CCOC1=CC=CC=C/C1=N\C(C)C MQSUJJCTCOKCCG-ACCUITESSA-N 0.000 description 1
- AWUMFQREGHLKJB-UHFFFAOYSA-N Cc(cc1)ccc1S(OC1=CC=CC=CC1=O)(=O)=O Chemical compound Cc(cc1)ccc1S(OC1=CC=CC=CC1=O)(=O)=O AWUMFQREGHLKJB-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a cycloheptatriene-base rare-earth metal catalyst, and a preparation method and application thereof, belonging to the field of catalysts. The method comprises the following steps: adding tropolone, paratoluensulfonyl chloride and triethylamine into a reactor, reacting in a nitrogen atmosphere for some time, adding amino substitute, reacting over night, recrystallizing to obtain a pure product, reacting with an Et3OBF4 solution for several hours, dropwisely adding the amino substitute, stirring over night, purifying by column chromatography to obtain a cycloheptatriene-base ligand; and dropwisely adding the ligand into an LnR3-dissolved toluene solution, stirring to react at room temperature for some time, filtering, concentrating, and recrystallizing to obtain the cycloheptatriene-base rare-earth metal catalyst. The catalyst has the advantage of accessible raw materials, and is applicable to polymerization reaction of multiple monomers, including homopolymerization and copolymerization of olefins, alkynes and polar monomers or copolymerization with CO2. The preparation method is simple, economical and environment-friendly, has wide application range, and is suitable for industrial 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 technical field.
Background technology
Conjugative effect refers to make due to interatomic influencing each other the π-electron in system (or p electronics) to distribute a kind of electronic effect changed in conjugated system, is a kind of important electronic effect in organic chemistry.It can make the distribution of cloud density in molecule change (copline), and interior energy reduces, and bond distance is tending towards equalization, and specific refractory power raises, and whole molecule is more stable.For structure and the property Quality Research thereof of these molecules, all have very important significance in theory with in practicality, therefore this compounds causes the broad interest of people.
Cycloheptatriene ylidene ligands is used in coordination chemistry field widely as non-luxuriant class part.This part is 10 π-electron systems of height conjugation, has started the frontier of non-benzenoid aromatic compound.In recent years, be subject to the extensive concern of scientists with the preparation of the cycloheptatriene base transition metal complex that is part all the time.The people such as Saman Damavandi report the application of cycloheptatriene base transition titanium metal catalyzer in olefinic polyreaction, the earliest for catalyzed ethylene polymerization.Philip J.Bailey research group has synthesized the cycloheptatriene Base Metal organic compound of magnesium, aluminium and indium; The people such as Brookhart have also synthesized the nickel metal complexes that cycloheptatriene ylidene ligands supports; The people such as Peter W.Roesky and Siegfried Blechert report calcium class, zinc class cycloheptatriene metal carbonyl complexes, and with its catalysis the hydroamination reaction of the substituent terminal olefine of band amido, have very high activity; The people such as Selvarajan Nagendran report the cycloheptatriene metal carbonyl complexes having synthesized germanium, and Nathan M.West research group successfully synthesizes the platinum title complex that cycloheptatriene ylidene ligands supports.In sum, the catalyzer that this part and part main group metal (as Zn, Mg, Ca, Al etc.) and transition metal (Ni, Ti, Pt etc.) synthesize obtains application in organic molecule reaction and vinyl polymerization.But the syntheti c route of cycloheptatriene metal carbonyl complexes is comparatively complicated, normally from cycloheptatriene ylidene ligands, react to slough the hydrogen atom on cycloheptatriene part at-78 DEG C with KH, then add metal halide reaction.This process reaction is consuming time longer, makes the method not possess the possibility of heavy industrialization process, therefore, those skilled in the art urgently wish to find more economy, environmental protection and be applicable to the industrialized method preparing cycloheptatriene metal carbonyl compound.At present, not yet someone reports for cycloheptatriene base rare-earth metal catalyst, preparation method and application in the polymerization thereof.
Summary of the invention
An object of the present invention is to provide a kind of cycloheptatriene base rare-earth metal catalyst; Two of object of the present invention is the preparation method providing a kind of cycloheptatriene base rare-earth metal catalyst; Three of object of the present invention is the application providing a kind of cycloheptatriene base rare-earth metal catalyst.
Object of the present invention is realized by following technical scheme:
A kind of cycloheptatriene base rare-earth metal catalyst, described cycloheptatriene base rare-earth metal catalyst structural formula have following I, II two kind:
In formula I, II, R
1, R
2and R
8it is the initiating group be connected with rare earth metal; L
1and L
2it is the coordinating group be connected with rare earth metal; R
4, R
10and R
10' be substituted radical in cycloheptatriene skeleton atom N; R
3, R
9and R
9' be substituted radical in cycloheptatriene skeleton double bond; R
5, R
6, R
7, R
11, R
11', R
12, R
12', R
13and R
13' be substituting group on cycloheptatriene ligand backbone; Ln
1, Ln
2it is rare earth metal;
Wherein, R
1, R
2, R
8one in equal preferred alkyl, trimethyl silicon based, amido, imido grpup, alkoxyl group, benzyl, cyclopentadienyl, indenyl, fluorenyl and halogen F, Cl, Br or I;
L
1, L
2one in preferred phosphide ligands (as triphenyl phosphorus), ethers part (as tetrahydrofuran (THF), ether), neutral amine ylidene ligands (as pyridine), imidazoles, carbazole, oxazole, DMF;
R
4preferably 2,6-dimethyl benzenes, 2,6-diisopropyl benzenes, 2-tert.-butylbenzene, 2-methyl-6-tert butyl benzene, 2,6-diphenyl benzene, penta fluoro benzene, 2, one in 6-dibromobenzene, 3,5-trifluoromethylbenzenes, 2-methylbenzene, 2-methyl-6-trifluoromethylbenzene, 2,6-difluorobenzenes;
R
10one in preferred sec.-propyl, the tertiary butyl, normal-butyl;
R
3preferably 2,6-xylidine, 2,6-diisopropyl aniline, 2-tertiary butyl aniline, 2-methyl-6-tert butyl aniline, 2,6-phenylbenzene aniline, penta fluoro benzene amine, 2,6-dibromo aniline, 3, one in 5-5-trifluoromethylaniline, 2-aminotoluene, 2-methyl-6-5-trifluoromethylaniline, 2,6-difluoroanilines;
R
9and R
9' one preferably in Sauerstoffatom, Isopropylamine, TERTIARY BUTYL AMINE;
R
5, R
11and R
11' one preferably in hydrogen atom, methyl, ethyl, alkoxyl group, sec.-propyl, the tertiary butyl, normal-butyl, nitro, amino, atomic iodine, bromine atoms, phenyl, benzyl, itrile group, sulfur phenenyl, anilino, phenylol, thiophenyl and 3,5-methylene fluoride thiophenyl;
R
6, R
7one in preferred phenyl, benzyl, anthryl, naphthyl, phenanthryl, sulfur phenenyl, anilino, phenylol, thiophenyl and 3,5-methylene fluoride thiophenyl;
R
12, R
12', R
13and R
13' one preferably in hydrogen atom, methyl, ethyl, sec.-propyl, the tertiary butyl, normal-butyl, alkoxyl group, itrile group, amino, atomic iodine, bromine atoms, nitro, itrile group;
Ln
1, Ln
2preferred scandium (Sc), lutetium (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 preparation method for cycloheptatriene base rare-earth metal catalyst, described method steps is as follows:
(1) cycloheptatriene ylidene ligands is prepared;
First, take tropolone, Tosyl chloride in reactor, add good solvent under room temperature, the preferred methylene dichloride of good solvent, starts to stir the mixture, more dropwise adds triethylamine in mixture, now will produce yellow muddy material; Separately add good solvent diluting reaction again; At room temperature under the atmosphere of nitrogen protection, after stir about 32h, obtain compound a.Wherein the mol ratio of tropolone, Tosyl chloride and triethylamine is 1:1:1;
Secondly, at low temperatures, amido substituent is slowly added dropwise in a; Mixture at room temperature stirs and spends the night.After carrying out recrystallization with good solvent and poor solvent, namely obtain the product b containing double bond O;
Finally, by the CH of b product
2cl
2solution slowly joins Et
3oBF
4in solution, after at room temperature stirring certain hour, then amido substituent is added dropwise in above-mentioned reaction flask slowly, after question response returns to room temperature, stirring is spent the night, and obtains the mixture c containing target product; In mixture c, add good solvent 25 ~ 35mL, layering obtains aqueous phase and organic phase, after adding solid drier 5 ~ 10g, filters, is spin-dried for, obtains crude product in organic phase.Described cycloheptatriene ylidene ligands is obtained again by the method for column chromatography purification product;
(2) cycloheptatriene base rare-earth metal catalyst is prepared;
First, reactor is placed in glove box, dropwise being joined by described for step (1) cycloheptatriene part is dissolved with in the solution of source metal, stirred at ambient temperature reaction 6h, obtain mixture, described mixture is filtered, get gained liquid and concentrate, obtain the thick product of cycloheptatriene base rare earth catalyst, obtain cycloheptatriene base rare-earth metal catalyst by after described thick product recrystallization;
Wherein, temperature of reaction is 20 ~ 25 DEG C, and the mol ratio of cycloheptatriene ylidene ligands and source metal is 1:1 or 2:1; The preferred methylene dichloride of good solvent in step (1); Preferred anhydrous magnesium sulfate (MgSO
4) drying is carried out to described organic phase; Source metal preferably two tetrahydrofuran (THF)-three (trimethyl silicane methyl)-rare earth compounds in step (2), molecular formula is [Ln (CH
2siMe
3)
3(THF)
2];
A kind of application of cycloheptatriene base rare-earth metal catalyst, described cycloheptatriene base rare-earth metal catalyst and alkyllithium reagent and organic boron salt form catalyst system, for homopolymerization and the copolymerization of catalyzed alkene, alkynes, polar monomer, or alkene, alkynes, polar monomer respectively with CO
2copolyreaction;
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 AlR
3aluminum alkyls, molecular formula be HAlR
2alkyl-al hydride, molecular formula be AlR
2one in the alkyl aluminum chloride of Cl or aikyiaiurnirsoxan beta, R is alkyl;
The step of described homopolymerization is as follows:
Reaction flask is placed in glove box, in reaction flask, adds described cycloheptatriene base rare earth catalyst successively, 5 ~ 10mL good solvent, aluminum alkyls, alkene, alkynes or polar monomer, organic boron salt, after under agitation reacting 0.3 ~ 6h, reaction flask is taken out, adds chain terminator, make the stopping of reaction; Reaction solution is poured into sedimentation in ethanol, separate out solid matter, described solid matter is removed desolventizing to constant weight with vacuum drying oven at 30 DEG C, obtains homopolymerization products;
Wherein alkene, alkynes or polar monomer, alkyllithium reagent, the mol ratio of organic boron salt and cycloheptatriene base rare earth catalyst is 200 ~ 600:2 ~ 100:1 ~ 100:1; Temperature of reaction is 25 ~ 90 DEG C.
The step of described copolyreaction is as follows:
Reaction flask is placed in glove box, in reaction flask, adds described cycloheptatriene base rare earth catalyst successively, 1 ~ 40mL good solvent, aluminum alkyls, reactant a or reactant b, organic boron salt, after under agitation reacting 3 ~ 24h, reaction flask is taken out, adds chain terminator, make the stopping of reaction; Reaction solution is poured into sedimentation in ethanol, separate out solid matter, described solid matter is removed desolventizing to constant weight with vacuum drying oven at 30 DEG C, obtains copolymerization product;
Wherein, reactant a or reactant b, alkyllithium reagent, the mol ratio of organic boron salt and cycloheptatriene base rare earth catalyst is 200 ~ 5000:2 ~ 100:1 ~ 100:1; Temperature of reaction is 25 ~ 70 DEG C; Reactant a is two kinds in branched-chain alkene, cycloolefin, alkynes, polar monomer, and reactant b is one in branched-chain alkene, cycloolefin, alkynes, polar monomer and CO
2.
One in the preferred trimethyl aluminium of described aluminum alkyls, triethyl aluminum, tri-n-n-propyl aluminum, three n-butylaluminum, triisopropylaluminiuand, triisobutyl aluminium, three hexyl aluminium, thricyclohexyl aluminium, trioctylaluminum, triphenyl aluminum, three p-methylphenyl aluminium, tribenzyl aluminium, ethyl dibenzyl aluminium, ethyl di-p-tolyl aluminium and diethylbenzyl aluminium;
One in described alkyl-al hydride preferred hydrogenation dimethyl aluminium, diethyl aluminium hydride, hydrogenation diη-propyl aluminium, hydrogenation di-n-butyl aluminium, hydrogenation di-isopropyl aluminium, diisobutylaluminium hydride, hydrogenation diamyl aluminium, hydrogenation dihexyl aluminium, hydrogenation dicyclohexyl aluminium, hydrogenation dioctyl aluminium, hydrogenated diphenyl aluminium, hydrogenation di-p-tolyl aluminium, hydrogenation dibenzyl aluminium, ethyl hydride benzyl aluminium and ethyl hydride p-methylphenyl aluminium;
Described alkyl aluminum chloride is preferred: the one in chlorodimethylalumiu, diethylaluminum chloride, chlorination diη-propyl aluminium, chlorination di-n-butyl aluminium, chlorination di-isopropyl aluminium, di-isobutyl aluminum chloride, chlorination diamyl aluminium, chlorination dihexyl aluminium, chlorination dicyclohexyl aluminium, chlorination dioctyl aluminium, diphenyl antimony chloride base aluminium, chlorination di-p-tolyl aluminium, chlorination dibenzyl aluminium, tonsilon benzyl aluminium and tonsilon p-methylphenyl aluminium;
Described aikyiaiurnirsoxan beta is preferred: the one in methylaluminoxane, ethylaluminoxane, n-propyl aikyiaiurnirsoxan beta and normal-butyl aikyiaiurnirsoxan beta;
The described preferred triphenyl of organic boron salt (methyl)-four (penta fluoro benzene) boron salt ([Ph
3c] [B (C
6f
5)
4]), amino-four (penta fluoro benzene) boron salt of phenyl-dimethyl ([PhMe
2nH] [B (C
6f
5)
4]), phenyl-dimethyl amino-tetraphenyl boron salt ([PhMe
2nH] [BPh
4]) or three (penta fluoro benzene) boron salt (B (C
6f
5)
3) in one;
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, vinylbenzene, alpha-methyl styrene, 3-1-chloro-4-methyl-benzene, 1,3-divinyl, isoprene, 1,3-cyclohexadiene, 1, one in 5-pentadiene, 1,6-hexadiene and Vinylstyrene;
One in the preferred norbornylene of described cycloolefin, polarity norbornylene, norbornadiene, ethylidene norbornene, phenyl norbornene, vinyl norbornene and dicyclopentadiene;
The preferred acetylene of described alkynes, phenylacetylene, to the one in phenylacetylene and diacetylene aromatic hydrocarbons;
Described polar monomer is divided into epoxy alkane and lactone, wherein epoxy alkane optimization ethylene oxide, propylene oxide, 1,2-butylene oxide ring, 2,3-butylene oxide ring, different butylene oxide ring, epoxy chloropropane, epoxy bromopropane, methyl glycidyl ether, glycidyl allyl ether, butylglycidyl ether, 2-ethyl hexylen glycidyl ether, trifluoro-epoxy propane, lactone is the one in 6-caprolactone, beta-butyrolactone, δ-valerolactone, rac-Lactide, glycollide and 3-methyl-glycollide;
Described chain terminator is preferably containing the ethanol of 5%2,6-di-tert-butyl-4-methy phenol, and in the volume of ethanol for 100%, wherein, volume ratio shared by 2,6 di tert butyl 4 methyl phenol is 5%; The preferred toluene of good solvent.
Beneficial effect
(1) cycloheptatriene base rare-earth metal catalyst of the present invention, be initial feed with tropolone, raw 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, economical efficiency is high, the feature of environmental protection good, is applicable to suitability for industrialized production;
(3) catalyst system of cycloheptatriene base rare-earth metal catalyst of the present invention, alkyllithium reagent and organic boron salt composition, can carry out branched-chain alkene, cycloolefin, alkynes, the homopolymerization of polar monomer and copolyreaction or branched-chain alkene, cycloolefin, alkynes, polar monomer and CO
2copolyreaction, obtain a series of new polymeric materials with ad hoc structure;
(4) cycloheptatriene base rare-earth metal catalyst of the present invention, when catalysis L-rac-Lactide and 6-caprolactone polymerization, can make the productive rate of the homopolymerization of 6-caprolactone reach 74.9%, can reach 100% to the productive rate of the homopolymerization of L-rac-Lactide.
(5) cycloheptatriene base rare-earth metal catalyst of the present invention, when catalysis isoprene polymerization, productive rate can reach 100%, and the selectivity along Isosorbide-5-Nitrae-structure reaches as high as 94.34%.This is a kind of novel synthetic polyisoprene material not yet reported, will contribute to for it finds suitable application purpose the further research of its physico-chemical property.
Accompanying drawing explanation
Accompanying drawing is the crystalline structure figure that the X-ray single crystal diffraction of cycloheptatriene base scandium catalyzer in embodiment 1 characterizes.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention will be further described, but be not limited thereto.
The main agents information mentioned in following examples is in table 1; Key instrument and facility information are in table 2.
Table 1
Table 2
In following examples, polymerization activity is by formula Activity=(myeild)/(n
cattime) calculate.Wherein, Activity is living polymerization, and unit is kgmol
-1h
-1, m is branched-chain alkene, cycloolefin, alkynes, polar monomer or CO
2quality, yield is productive rate, n
catfor the amount of catalyst substance, time is the polymerization time used.
Polyisoprene microtexture can be by
1h-NMR and
13c-NMR spectrogram provides, and selectivity specific formula for calculation is as follows:
(1) selectivity (proportion) of Isosorbide-5-Nitrae-polyisoprene:
Mol 1,4-IP％＝{I
H1/(I
H1+0.5I
H2)}×100
The selectivity (proportion) of (2) 3,4-polyisoprene:
Mol 3,4-IP％＝{0.5I
H2/(I
H1+0.5I
H2)}×100
(3) along the selectivity (proportion) of Isosorbide-5-Nitrae-polyisoprene:
Mol cis-1,4-IP％＝{I
C1/(I
C1+I
C2+I
C3)}×100
(4) selectivity (proportion) of anti-Isosorbide-5-Nitrae-polyisoprene:
Mol trans-1,4-IP％＝{I
C3/(I
C1+I
C2+I
C3)}×100
The selectivity (proportion) of (5) 3,4-polyisoprene:
Mol 3,4-IP％＝{I
C2/(I
C1+I
C2+I
C3)}×100
Wherein, IP is polyisoprene, I
h1for
1the integration at 5.13ppm place in H spectrum; I
h2for
1the integration at 4.72ppm place in H spectrum; I
c1for
13the integration at 23.2ppm place in C spectrum; I
c2for
13the integration at 18.5ppm place in C spectrum; I
c3for
13the integration at 15.9ppm place in C spectrum.
Embodiment 1
(1) cycloheptatriene ylidene ligands is prepared
First, take tropolone 5.3g (43mmol) and Tosyl chloride 8.2g (43mmol) in reactor, 60mL methylene dichloride is added under room temperature, start to stir the mixture, in mixture, dropwise add 6mL (43mmol) triethylamine again, now will produce yellow muddy material.Separately add 60mL methylene dichloride again.At room temperature under the atmosphere of nitrogen protection, after stir about 32h, obtain compound a.
Secondly, at low temperatures, Isopropylamine (60mL) is slowly added dropwise in a (10.92g, 40.0mmol).After mixture at room temperature stirs and spends the night, vacuum rotary steam, the material 2mol/L NaOH (60mL) obtained and CH
2cl
2(120mL) dissolve, layering, isolates organic phase.Aqueous phase uses CH again
2cl
2(120mL) 2 times are extracted.Merge organic phase, with the washing of 20mL strong brine, and use anhydrous MgSO
4drying, suction filtration, filtrate is spin-dried for, the solid CH obtained
2cl
2after carrying out recrystallization with normal hexane, obtain yellow solid b, be cycloheptatriene ylidene ligands, productive rate is 80.9%.
(2) cycloheptatriene base scandium catalyzer is prepared
First, reactor is placed in glove box, cycloheptatriene part (665.9mg, 4.08mmol) prepared by step (1) is dropwise joined and is dissolved with Sc (CH
2siMe
3)
3(thf)
2in the toluene solution of (920mg, 2.04mmol), under agitation react 6h, obtain mixture c; Wherein, temperature of reaction is 25 DEG C;
Secondly, filtered by described mixture c, get gained liquid and concentrate, obtain the thick product of cycloheptatriene base scandium catalyzer, obtain yellow powder 0.720g by after described thick product recrystallization, be cycloheptatriene base scandium catalyzer d, productive rate is 65%.Be the crystalline structure figure that the X-ray single crystal diffraction of cycloheptatriene base scandium catalyzer d characterizes as shown in drawings.
The application that following examples 5 ~ embodiment 11 and embodiment 16 ~ embodiment 18 are the cycloheptatriene base scandium catalyzer d described in embodiment 1.
Embodiment 2
(1) cycloheptatriene ylidene ligands is prepared
First, take tropolone 5.3g (43mmol) and Tosyl chloride 8.2g (43mmol) in reactor, 60mL methylene dichloride is added under room temperature, 4.4g (6mL is dropwise added again in mixture, 43mmol) triethylamine, separately adds 60mL methylene dichloride again.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)
2cl
2solution slowly joins Et
3oBF
4(1.75g, 9.21mmol) in solution, after at room temperature stirring 3h, point plate, until when new product point no longer changes, be cooled to 0 DEG C by reaction, again Isopropylamine (20mL) is added dropwise in above-mentioned reaction flask slowly, after question response returns to room temperature, stirring is spent the night, and obtains the Mischung containing target product.Oily mater after vacuum rotary steam NaOH (10mL) and CH
2cl
2(20mL) dissolve, be separated organic phase.Aqueous phase CH
2cl
2(20mL) 2 times are extracted.Merge organic phase, with the washing of 20mL strong brine, and use anhydrous MgSO
4dry.Suction filtration, is spin-dried for.Obtain crude product.Obtain cycloheptatriene ylidene ligands f described in 1.39g by the method for column chromatography purification product again, productive rate is 47.9%.
(2) cycloheptatriene base scandium catalyzer is prepared
First, reactor is placed in glove box, cycloheptatriene ylidene ligands f (613.0mg, 3mmol) prepared by step (1) is dropwise joined and is dissolved with Sc (CH
2siMe
3)
3(thf)
2in the toluene solution of (676.2mg, 1.5mmol), under agitation react 6h, obtain mixture g; Wherein, temperature of reaction is 25 DEG C;
Secondly, after being filtered by described mixture g, concentrate, obtain the thick product of cycloheptatriene base scandium catalyzer, obtain yellow powder 0.530g by after described thick product recrystallization, be cycloheptatriene base scandium catalyzer h, productive rate is 58%.
Following examples 12 ~ 15 are the aggregated application of the cycloheptatriene base scandium catalyzer h described in embodiment 2.
Embodiment 3
(1) cycloheptatriene ylidene ligands is prepared
The operation of compound a, b is with embodiment 1.Afterwards, by the CH of b product (1.37g, 9.20mmol)
2cl
2solution slowly joins Et
3oBF
4(1.75g, 9.21mmol) in solution, after at room temperature stirring 3h, some plate, defines new product and generates, until when new product point no longer changes, reaction is cooled to 0 DEG C, then Isopropylamine (20mL) is added dropwise in above-mentioned reaction flask, after question response returns to room temperature with the speed that 1s/ drips slowly, stirring is spent the night, and obtains the Mischung containing target product.Obtain cycloheptatriene ylidene ligands f described in 1.39g by the method for column chromatography purification product again, productive rate is 47.9%.
(2) cycloheptatriene base lutetium catalyzer is prepared
First, reactor is placed in glove box, cycloheptatriene ylidene ligands f (326.9mg, 3.0mmol) prepared by step (1) is dropwise joined and is dissolved with Lu (CH
2siMe
3)
3(thf)
2in the toluene solution of (676.2mg, 1.5mmol), under agitation react 6h, obtain mixture i; Wherein, temperature of reaction is 25 DEG C;
Secondly, after being filtered by described mixture i, concentrate, obtain the thick product of cycloheptatriene base lutetium catalyzer, described thick product is obtained at-33 DEG C the cycloheptatriene base lutetium catalyzer j of 0.699g after recrystallization, productive rate is 63%.
Embodiment 4
(1) cycloheptatriene ylidene ligands is prepared
The operation of compound a is with embodiment 1.Afterwards, at 0 DEG C, Isopropylamine (60mL) is slowly added dropwise in a (10.92g, 40.0mmol).Mixture at room temperature stirs and spends the night.The solid CH that aftertreatment obtains
2cl
2after carrying out recrystallization with normal hexane, obtain yellow solid b.Finally, by the CH of b product (1.37g, 9.20mmol)
2cl
2solution slowly joins Et
3oBF
4(1.75g, 9.21mmol) in solution, after at room temperature stirring 3h, point plate, when defining new product generation, is cooled to 0 DEG C by reaction, again Isopropylamine (20mL) is added dropwise in above-mentioned reaction flask slowly, after question response returns to room temperature, stirring is spent the night, and obtains the Mischung containing target product.Obtain cycloheptatriene ylidene ligands f described in 1.39g by the method for column chromatography purification product again, productive rate is 47.9%.
(2) cycloheptatriene base yttrium catalyzer is prepared
First, reactor is placed in glove box, cycloheptatriene ylidene ligands f (1175.2mg, 4.7mmol) prepared by step (1) is dropwise joined and is dissolved with Y (CH
2siMe
3)
3(thf)
2in the toluene solution of (1162.8mg, 2.4mmol), under agitation react 6h, obtain mixture k; Wherein, temperature of reaction is 25 DEG C;
Secondly, after being filtered by described mixture k, concentrate, obtain the thick product of cycloheptatriene base lutetium catalyzer, described thick product is obtained at-33 DEG C the cycloheptatriene base lutetium catalyzer l of 0.989g after recrystallization, productive rate is 63%.
Embodiment 5
Reactor is placed in glove box, in eggplant bottle, adds 20 μm of ol cycloheptatriene base scandium catalyzer d successively, 40 μm of ol's
iprOH, add 2mL THF, after stirring at room temperature 10 ~ 30min, by the THF solution of 3mL containing 8mmol L-rac-Lactide, then add in catalyst mixture, stirring reaction 2.5h, temperature of reaction 25 DEG C, become after thickness until solution, add the ethanolic soln stopped reaction of the HCl of volume fraction 10%, then pour sedimentation in ethanol into, filter, washing obtains white polymer, by the vacuum-drying at 30 DEG C of described solid matter, except desolventizing is to constant weight, obtain polylactide, net weight 0.055g, transformation efficiency 5.8%, polymerization activity is 1.64kgmol
-1h
-1; The number-average molecular weight M of gpc analysis polylactide
n=23 × 10
4, molecular weight distribution M
w/ M
n=1.58.
Embodiment 6
Reactor is placed in glove box, and in eggplant bottle, add 20 μm of ol cycloheptatriene base scandium catalyzer d successively, the EtONa of 40 μm of ol, adds the CH of 2mL
2cl
2, after stirring at room temperature 10 ~ 30min, by the CH of 3mL containing 8mmol L-rac-Lactide
2cl
2solution, then add in catalyst mixture, stirring reaction 2.5h, temperature of reaction 25 DEG C, all the other operations are with embodiment 5, and obtain polylactide, net weight 1.179g, transformation efficiency is 100%, and polymerization activity is 23.58kgmol
-1h
-1; The number-average molecular weight M of gpc analysis polylactide
n=15 × 10
4, molecular weight distribution M
w/ M
n=1.31.
Embodiment 7
Reactor is placed in glove box, in eggplant bottle, add 20 μm of ol cycloheptatriene base scandium catalyzer d successively, the EtONa of 40 μm of ol, adds the THF of 2mL, after stirring 10 ~ 30min, by the THF solution of 3mL containing 8mmol 6-caprolactone, then add in catalyst mixture, stirring reaction 2.5h, all the other operations are with embodiment 5, obtain polycaprolactone 0.683g, transformation efficiency is 74.9%, and polymerization activity is 13.68kgmol
-1h
-1; The number-average molecular weight M of gpc analysis polycaprolactone
n=9 × 10
4, molecular weight distribution M
w/ M
n=1.69.
Embodiment 8
Reactor is placed in glove box, and in eggplant bottle, add 20 μm of ol cycloheptatriene base scandium catalyzer d successively, the EtONa of 40 μm of ol, adds the CH of 2mL
2cl
2, after stirring 10 ~ 30min, 3mL is contained the CH of the L-rac-Lactide of 4mmol and the 6-caprolactone of 4mmol
2cl
2solution, then add in catalyst mixture, stirring reaction 4h, all the other operations are with embodiment 5, and obtain the multipolymer of L-rac-Lactide and 6-caprolactone, net weight 0.859g, polymerization activity is 34.36kgmol
-1h
-1; The number-average molecular weight M of gpc analysis multipolymer
n=8 × 10
4, molecular weight distribution M
w/ M
n=1.33.
Embodiment 9
Reactor is placed in glove box, in eggplant bottle, adds 25 μm of ol cycloheptatriene base scandium catalyzer d successively, 5mL toluene, 50 μm of ol Al
ibu
3, 5mmol phenylacetylene and 25 μm of ol [PhNHMe
2] [B (C
6f
5)
4], react 0.3h at 50 DEG C after, eggplant bottle is taken out, add the ethanol of 30mL containing 5%2,6-di-tert-butyl-4-methy phenol, make the stopping of reaction; Reaction solution ethanol is carried out sedimentation, separates out white solid matter, by the vacuum-drying at 30 DEG C of described solid matter, except desolventizing is to constant weight, obtain polyphenylacetylene, net weight 0.29g, transformation efficiency 57%; The number-average molecular weight M of gpc analysis polyphenylacetylene
n=2 × 10
4, molecular weight distribution M
w/ M
n=1.73.
Embodiment 10
Reactor is placed in glove box, in eggplant bottle, adds 25 μm of ol cycloheptatriene scandium catalyzer d successively, 5mL toluene, 50 μm of ol AlMe
3, 5mmol propylene oxide and 25 μm of ol [Ph
3c] [B (C
6f
5)
4], reaction times 5h, temperature of reaction 50 DEG C, all the other operations, with embodiment 9, obtain poly(propylene oxide), net weight 0.26g, transformation efficiency 90%; The number-average molecular weight M of gpc analysis poly(propylene oxide)
n=17 × 10
4, molecular weight distribution M
w/ M
n=1.62.
Embodiment 11
Reactor is placed in glove box, in eggplant bottle, adds 21 μm of ol cycloheptatriene base scandium catalyzer d successively, 25mL toluene, 42 μm of ol Al
ibu
3, 53mmol norbornylene, 53mmol Isosorbide-5-Nitrae-divinyl, and 21 μm of ol [Ph
3c] [B (C
6f
5)
4], reaction times 3h, temperature of reaction 25 DEG C, all the other operations, with embodiment 9, obtain the multipolymer of norbornylene and Isosorbide-5-Nitrae-divinyl, transformation efficiency 79%; The number-average molecular weight M of gpc analysis multipolymer
n=3.5 × 10
4, molecular weight distribution M
w/ M
n=1.69.
Embodiment 12
Reactor is placed in glove box, in eggplant bottle, adds 25 μm of ol cycloheptatriene base scandium catalyzer h successively, 5mL toluene, 50 μm of ol Al
ibu
3, 15mmol isoprene and 25 μm of ol [Ph
3c] [B (C
6f
5)
4], the reaction times is 6h, temperature of reaction 25 DEG C, and all the other operations are with embodiment 9, and obtain polyisoprene, net weight 0.714g, transformation efficiency 70%, polymerization activity is 4.8kgmol
-1h
-1; The number-average molecular weight of gpc analysis polyisoprene is Mn=10 × 10
3, molecular weight distribution M
w/ M
n=1.54; Suitable Isosorbide-5-Nitrae-polymerization selectivity is 84%.
Embodiment 13
Reactor is placed in glove box, in eggplant bottle, adds 25 μm of ol cycloheptatriene base scandium catalyzer h successively, 5mL toluene, 50 μm of ol Al
ibu
3, 5mmol isoprene and 25 μm of ol [Ph
3c] [B (C
6f
5)
4], the reaction times is 6h, temperature of reaction 25 DEG C, and all the other operations are with embodiment 9, and obtain polyisoprene, net weight 0.335g, transformation efficiency 98.5%, polymerization activity is 2.2kgmol
-1h
-1; The number-average molecular weight of gpc analysis polyisoprene is Mn=15 × 10
3, molecular weight distribution M
w/ M
n=1.76; Suitable Isosorbide-5-Nitrae-polymerization selectivity is 94.34%.
Embodiment 14
Reactor is placed in glove box, in eggplant bottle, adds 25 μm of ol cycloheptatriene base scandium catalyzer h successively, 10mL toluene, 2.5mmol Al
ibu
3, 5mmol isoprene and 2.5mmol [PhNHMe
2] [B (C
6f
5)
4], reaction times 3h, temperature of reaction 25 DEG C, all the other operations are with embodiment 9, and obtain polyisoprene, net weight 0.306g, transformation efficiency 90%, polymerization activity is 4.1kgmol
-1h
-1; The number-average molecular weight of gpc analysis polyisoprene is Mn=18 × 10
3, molecular weight distribution M
w/ M
n=1.98; Along Isosorbide-5-Nitrae-polymerization selectivity 89%.
Embodiment 15
Reactor is placed in glove box, in eggplant bottle, adds 25 μm of ol cycloheptatriene base scandium catalyzer h successively, 10mL toluene, 2.5mmol Al
ibu
3, 5mmol isoprene and 2.5mmol [PhNHMe
2] [B (C
6f
5)
4], reaction times 3h, temperature of reaction 90 DEG C, all the other operations are with embodiment 9, and obtain polyisoprene, net weight 0.34g, transformation efficiency 100%, polymerization activity is 4.5kgmol
-1h
-1; The number-average molecular weight of gpc analysis polyisoprene is Mn=12 × 10
3, molecular weight distribution M
w/ M
n=2.27; Along Isosorbide-5-Nitrae-polymerization selectivity 76%.
Embodiment 16
Reactor is placed in glove box, takes 2g norbornene monomer with the bottle that 20mL is clean and be put in 50mL eggplant bottle, add 4.57mL toluene, add 0.5 μm of ol cycloheptatriene base scandium catalyzer d with syringe, drip AlMe
3toluene solution 8 μ L.After 1h, take out glove box acidic ethanol (ethanol: concentrated hydrochloric acid=20:1) 30mL DeR liquid, filter, and leach solid by washing with alcohol; After being pulverized by solid, vacuum drying oven 30 DEG C of vacuum-dryings, except desolventizing is to constant weight, obtain polynorbornene 0.04g, productive rate 2.0%, and polymerization activity is 40.0kgmol as far as possible
-1h
-1; The number-average molecular weight of gpc analysis polynorbornene is Mn=15 × 10
3, molecular weight distribution M
w/ M
n=1.27.
Embodiment 17
Reactor is placed in glove box, in eggplant bottle, adds 25 μm of ol cycloheptatriene base scandium catalyzer d successively, 5mL toluene, 250 μm of ol Al
ibu
3, 10mmol vinylbenzene and 25 μm of ol [Ph
3c] [B (C
6f
5)
4], the reaction times is 4h, temperature of reaction 25 DEG C.All the other operations, with embodiment 9, obtain polystyrene; Net weight 0.382g, transformation efficiency 36.7%, polymerization activity is 3.82kgmol
-1h
-1; The number-average molecular weight of gpc analysis polystyrene is Mn=90 × 10
3, molecular weight distribution M
w/ M
n=1.49.
Embodiment 18
Reactor is placed in glove box, and in eggplant bottle, add 50 μm of ol cycloheptatriene base scandium catalyzer d successively, 1mL toluene, 20mol propylene oxide, sealed reactor, migrates out glove box, in reactor, pass into CO
2, regulate pressure to 6Mpa, be then heated to 70 DEG C, reaction 24h, is then cooled to room temperature, dissolves, add methyl alcohol and obtain white solid with chloroform, with methanol wash column, vacuum drying, obtains propylene oxide and CO
2multipolymer; Productive rate is 43.0%, and molecular weight is M
n=31 × 10
3, molecular weight distribution M
w/ M
n=1.40.
The present invention includes but be not limited to above embodiment, every any equivalent replacement of carrying out under the principle of spirit of the present invention or local improvement, all will be considered as within protection scope of the present invention.
Claims (9)
1. a cycloheptatriene base rare-earth metal catalyst, is characterized in that: described cycloheptatriene base rare-earth metal catalyst structural formula have following I, II two kind:
Wherein, R
1, R
2and R
8it is the initiating group be connected with rare earth metal; L
1and L
2it is the coordinating group be connected with rare earth metal; R
4, R
10and R
10' be substituted radical in cycloheptatriene skeleton atom N; R
3, R
9and R
9' be substituted radical in cycloheptatriene skeleton double bond; R
5, R
6, R
7, R
11, R
11', R
12, R
12', R
13and R
13' be substituting group on cycloheptatriene ligand backbone; Ln
1, Ln
2it is rare earth metal.
2. cycloheptatriene base rare-earth metal catalyst according to claim 1, is characterized in that:
R
1, R
2, R
8be the one in alkyl, trimethyl silicon based, amido, imido grpup, alkoxyl group, benzyl, cyclopentadienyl, indenyl, fluorenyl and halogen F, Cl, Br or I;
L
1, L
2be the one in phosphide ligands (as triphenyl phosphorus), ethers part (as tetrahydrofuran (THF), ether), neutral amine ylidene ligands (as pyridine), imidazoles, carbazole, oxazole, DMF;
R
4be 2,6-dimethyl benzene, 2,6-diisopropyl benzenes, 2-tert.-butylbenzene, 2-methyl-6-tert butyl benzene, 2,6-diphenyl benzene, penta fluoro benzene, 2, one in 6-dibromobenzene, 3,5-trifluoromethylbenzenes, 2-methylbenzene, 2-methyl-6-trifluoromethylbenzene, 2,6-difluorobenzenes;
R
10for the one in sec.-propyl, the tertiary butyl, normal-butyl;
R
3be 2,6-xylidine, 2,6-diisopropyl aniline, 2-tertiary butyl aniline, 2-methyl-6-tert butyl aniline, 2,6-phenylbenzene aniline, penta fluoro benzene amine, 2,6-dibromo aniline, 3, one in 5-5-trifluoromethylaniline, 2-aminotoluene, 2-methyl-6-5-trifluoromethylaniline, 2,6-difluoroanilines;
R
9and R
9' be one in Sauerstoffatom, Isopropylamine, TERTIARY BUTYL AMINE; Wherein, R
9and R
9' identical;
R
5, R
11and R
11' be one in hydrogen atom, methyl, ethyl, alkoxyl group, sec.-propyl, the tertiary butyl, normal-butyl, nitro, amino, atomic iodine, bromine atoms, phenyl, benzyl, itrile group, sulfur phenenyl, anilino, phenylol, thiophenyl and 3,5-methylene fluoride thiophenyl; Wherein, R
11and R
11' identical;
R
6, R
7be the one in phenyl, benzyl, anthryl, naphthyl, phenanthryl, sulfur phenenyl, anilino, phenylol, thiophenyl and 3,5-methylene fluoride thiophenyl;
R
12, R
12', R
13and R
13' be one in hydrogen atom, methyl, ethyl, sec.-propyl, the tertiary butyl, normal-butyl, alkoxyl group, itrile group, amino, atomic iodine, bromine atoms, nitro, itrile group; Wherein, R
12and R
12' identical, R
13and R
13' identical;
Ln
1, Ln
2be scandium (Sc), lutetium (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).
3. a preparation method for the cycloheptatriene base rare-earth metal catalyst as described in claim 1,2, is characterized in that: described method steps and condition as follows:
(1) cycloheptatriene ylidene ligands is synthesized:
First, take tropolone, Tosyl chloride in reactor, under room temperature, add good solvent, the preferred methylene dichloride of good solvent, starts to stir the mixture, more dropwise adds triethylamine in mixture, now will produce yellow muddy material, separately add good solvent diluting reaction again; At room temperature under the atmosphere of nitrogen protection, after stir about 32h, obtain compound a; Wherein the mol ratio of tropolone, Tosyl chloride and triethylamine is 1:1:1;
Secondly, at low temperatures, be slowly added dropwise in a by amido substituent, mixture at room temperature stirs and spends the night, and after carrying out recrystallization, namely obtains the product b containing double bond O with good solvent and poor solvent;
Finally, by the CH of b product
2cl
2solution slowly joins Et
3oBF
4in solution, after at room temperature stirring certain hour, then amido substituent is added dropwise in above-mentioned reaction flask slowly, after question response returns to room temperature, stirring is spent the night, and obtains the mixture c containing target product; In mixture c, add good solvent 25 ~ 35mL, layering obtains aqueous phase and organic phase, after adding solid drier 5 ~ 10g, filters, is spin-dried for, obtains crude product in organic phase.Described cycloheptatriene ylidene ligands is obtained again by the method for column chromatography purification product;
(2) cycloheptatriene base rare-earth metal catalyst is prepared:
First, reactor is placed in glove box, dropwise being joined by described for step (1) cycloheptatriene part is dissolved with in the solution of source metal, stirred at ambient temperature reaction 6h, obtain mixture, described mixture is filtered, get gained liquid and concentrate, obtain the thick product of cycloheptatriene base rare earth catalyst, obtain cycloheptatriene base rare-earth metal catalyst by after described thick product recrystallization.
4. the preparation method of cycloheptatriene base rare-earth metal catalyst as claimed in claim 3, is characterized in that: in step (1), solid drier is anhydrous magnesium sulfate; In step (2), source metal is two tetrahydrofuran (THF)-three (trimethyl silicane methyl)-rare earth compounds, and molecular formula is [Ln (CH
2siMe
3)
3(THF)
2], described Ln is the one in scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium; Me is methyl; THF is tetrahydrofuran (THF).
5. the application of the cycloheptatriene base rare-earth metal catalyst described in a claim 1,2, it is characterized in that: described cycloheptatriene base rare-earth metal catalyst and alkyllithium reagent and organic boron salt form catalyst system, for homopolymerization and the copolymerization of catalyzed alkene, alkynes, polar monomer, or alkene, alkynes, polar monomer respectively with CO
2copolyreaction;
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 AlR
3aluminum alkyls, molecular formula be HAlR
2alkyl-al hydride, molecular formula be AlR
2one in the alkyl aluminum chloride of Cl or aikyiaiurnirsoxan beta, R is alkyl.
6. the application of a kind of cycloheptatriene base rare-earth metal catalyst according to claim 5, is characterized in that: the step of described homopolymerization is as follows:
Reaction flask is placed in glove box, in reaction flask, adds described cycloheptatriene base rare earth catalyst successively, 5 ~ 10mL good solvent, aluminum alkyls, alkene, alkynes or polar monomer, organic boron salt, after under agitation reacting 0.3 ~ 6h, reaction flask is taken out, adds chain terminator, make the stopping of reaction; Reaction solution is poured into sedimentation in ethanol, separate out solid matter, described solid matter is removed desolventizing to constant weight with vacuum drying oven at 30 DEG C, obtains homopolymerization products;
Wherein alkene, alkynes or polar monomer, alkyllithium reagent, the mol ratio of organic boron salt and cycloheptatriene base rare earth catalyst is 200 ~ 600:2 ~ 100:1 ~ 100:1; Temperature of reaction is 25 ~ 90 DEG C.
7. the application of a kind of cycloheptatriene base rare-earth metal catalyst according to claim 5, is characterized in that: the step of described copolyreaction is as follows:
Reaction flask is placed in glove box, in reaction flask, adds described cycloheptatriene base rare earth catalyst successively, 1 ~ 40mL good solvent, aluminum alkyls, reactant a or reactant b, organic boron salt, after under agitation reacting 3 ~ 24h, reaction flask is taken out, adds chain terminator, make the stopping of reaction; Reaction solution is poured into sedimentation in ethanol, separate out solid matter, described solid matter is removed desolventizing to constant weight with vacuum drying oven at 30 DEG C, obtains copolymerization product;
Wherein, reactant a or reactant b, alkyllithium reagent, the mol ratio of organic boron salt and cycloheptatriene base rare earth catalyst is 200 ~ 5000:2 ~ 100:1 ~ 100:1; Temperature of reaction is 25 ~ 70 DEG C; Reactant a is two kinds in branched-chain alkene, cycloolefin, alkynes, polar monomer, and reactant b is one in branched-chain alkene, cycloolefin, alkynes, polar monomer and CO
2.
8. the application of cycloheptatriene base rare-earth metal catalyst according to claim 5, is characterized in that:
Described aluminum alkyls is the one in trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, three n-butylaluminum, triisopropylaluminiuand, triisobutyl aluminium, three hexyl aluminium, thricyclohexyl aluminium, trioctylaluminum, triphenyl aluminum, three p-methylphenyl aluminium, tribenzyl aluminium, ethyl dibenzyl aluminium, ethyl di-p-tolyl aluminium and diethylbenzyl aluminium;
Described alkyl-al hydride is the one in hydrogenation dimethyl aluminium, diethyl aluminium hydride, hydrogenation diη-propyl aluminium, hydrogenation di-n-butyl aluminium, hydrogenation di-isopropyl aluminium, diisobutylaluminium hydride, hydrogenation diamyl aluminium, hydrogenation dihexyl aluminium, hydrogenation dicyclohexyl aluminium, hydrogenation dioctyl aluminium, hydrogenated diphenyl aluminium, hydrogenation di-p-tolyl aluminium, hydrogenation dibenzyl aluminium, ethyl hydride benzyl aluminium and ethyl hydride p-methylphenyl aluminium;
Described alkyl aluminum chloride is: the one in chlorodimethylalumiu, diethylaluminum chloride, chlorination diη-propyl aluminium, chlorination di-n-butyl aluminium, chlorination di-isopropyl aluminium, di-isobutyl aluminum chloride, chlorination diamyl aluminium, chlorination dihexyl aluminium, chlorination dicyclohexyl aluminium, chlorination dioctyl aluminium, diphenyl antimony chloride base aluminium, chlorination di-p-tolyl aluminium, chlorination dibenzyl aluminium, tonsilon benzyl aluminium and tonsilon p-methylphenyl aluminium;
Described aikyiaiurnirsoxan beta is: the one in methylaluminoxane, ethylaluminoxane, n-propyl aikyiaiurnirsoxan beta and normal-butyl aikyiaiurnirsoxan beta;
Described organic boron salt is triphenyl (methyl)-four (penta fluoro benzene) boron salt ([Ph
3c] [B (C
6f
5)
4]), amino-four (penta fluoro benzene) boron salt of phenyl-dimethyl ([PhMe
2nH] [B (C
6f
5)
4]), phenyl-dimethyl amino-tetraphenyl boron salt and three (penta fluoro benzene) boron salt ([PhMe
2nH] [BPh
4]) in one;
Described branched-chain alkene is ethene, propylene, 1-butylene, 1-amylene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-eicosylene, vinylbenzene, alpha-methyl styrene, 3-1-chloro-4-methyl-benzene, 1,3-divinyl, isoprene, 1,3-cyclohexadiene, 1, one in 5-pentadiene, 1,6-hexadiene and Vinylstyrene;
Described cycloolefin is the one in norbornylene, polarity norbornylene, norbornadiene, ethylidene norbornene, phenyl norbornene, vinyl norbornene and dicyclopentadiene;
Described alkynes be acetylene, phenylacetylene, to the one in phenylacetylene and diacetylene aromatic hydrocarbons;
Described polar monomer is divided into epoxy alkane and lactone, wherein epoxy alkane is oxyethane, propylene oxide, 1,2-butylene oxide ring, 2,3-butylene oxide ring, different butylene oxide ring, epoxy chloropropane, epoxy bromopropane, methyl glycidyl ether, glycidyl allyl ether, butylglycidyl ether, 2-ethyl hexylen glycidyl ether, trifluoro-epoxy propane, lactone is the one in 6-caprolactone, beta-butyrolactone, δ-valerolactone, rac-Lactide, glycollide and 3-methyl-glycollide.
9. the application of a kind of cycloheptatriene base rare-earth metal catalyst according to claim 6 or 7, it is characterized in that: described chain terminator is for containing 2, the ethanol of 6-di-tert-butyl-4-methy phenol, in the volume of ethanol for 100%, wherein, volume ratio shared by 2,6 di tert butyl 4 methyl phenol is 5%; Good solvent is toluene.
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| CN105126910A (en) * | 2015-07-23 | 2015-12-09 | 北京理工大学 | C2-symmetric imidazolephenyl rare earth metal catalyst, preparation method and application |
| CN110357926A (en) * | 2019-07-26 | 2019-10-22 | 广西师范大学 | Tropolone and phenanthroline mixture manganese complex and its preparation method and application |
| CN113461850A (en) * | 2021-08-13 | 2021-10-01 | 中国科学院长春应用化学研究所 | Trans-1, 4-poly (4, 8-2-methyl-1, 3, 7-nonane triene) and preparation method thereof |
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| CN105126910A (en) * | 2015-07-23 | 2015-12-09 | 北京理工大学 | C2-symmetric imidazolephenyl rare earth metal catalyst, preparation method and application |
| CN110357926A (en) * | 2019-07-26 | 2019-10-22 | 广西师范大学 | Tropolone and phenanthroline mixture manganese complex and its preparation method and application |
| CN113461850A (en) * | 2021-08-13 | 2021-10-01 | 中国科学院长春应用化学研究所 | Trans-1, 4-poly (4, 8-2-methyl-1, 3, 7-nonane triene) and preparation method thereof |
| CN113461850B (en) * | 2021-08-13 | 2022-03-29 | 中国科学院长春应用化学研究所 | Trans-1, 4-poly (4, 8-2-methyl-1, 3, 7-nonane triene) and preparation method thereof |
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