CN103936902B - A kind of triple phenoxyl bicyclic pentadiene titanium catalyst and its production and use - Google Patents
A kind of triple phenoxyl bicyclic pentadiene titanium catalyst and its production and use Download PDFInfo
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Abstract
A kind of triple phenoxyl bicyclic pentadiene titanium catalyst, belongs to high molecular polymerization catalyst field.The invention provides a kind of triple phenoxyl bicyclic pentadiene titanium catalyst and preparation thereof and utilize the problems such as its method of carrying out olefinic polymerization catalysis reaction is low with the charge capacity solving prior art existence, catalytic activity is low, preparation method is complicated, use cost is high.The present invention by reacting with the benzenetriol of phenyl bridging and strong alkaline substance the benzenetriol salt preparing phenyl bridging, then prepares triple phenoxyl bicyclic pentadiene titanium catalyst after reacting with xenyl bis-tetramethyl cyclopentadienyl titanous chloride.Triple phenoxyl bicyclic pentadiene titanium catalyst in the present invention can be used as the equal polyreaction of Primary Catalysts catalyzed alkene, due to the catalyzer that the present invention is from load, there is higher catalytic activity, therefore can reduce the usage quantity of promotor, reduce the cost that alkene is all polymerized.
Description
Technical field
The invention belongs to the technical field of high molecular polymerization catalyzer, be specifically related to a kind of triple phenoxyl bicyclic pentadiene titanium catalyst, relate to its method of preparation and use further.
Background technology
In recent years, in the research and development field of olefinic polymerization, metallocene catalyst shows the inaccessiable advantage of traditional catalyst, be mainly manifested in the structure by changing Primary Catalysts, substituting effect such as by regulating and controlling main part and assistant ligand just can realize the specific performance of catalysis in olefine polymerization, as the raising of catalytic reaction activity, the various parameters of regulation and control polymerisate, the vertical structure degree of such as polymer stacks density, molecular weight, molecular weight distribution, polymkeric substance, co-monomer content and composition distribution, the degree of branching, crystalline structure and fusing point etc.Can say that metallocene catalyst is the leap of technology again after Zieglar-Natta catalyzer, open the frontier of polyolefin resin, and provide possibility for developing extraordinary polyolefine material.But catalyzed by homogeneous metallocene catalyst olefin polymerization technology also has larger limitation simultaneously, as promotor consumption is large, polymkeric substance sticks the defects such as still.Current olefinic polymerization Methods for Immobilization of Metallocene Catalysts is the another effective ways solving olefin polymetiation process (vapour phase polymerization and slurry polymerization), limitation when polymkeric substance sticks the homogeneous catalytic olefin polymerization techniques such as still, promotor consumption be large can be overcome, and effectively can improve morphology.The effective carrier of the load metallocene catalyst be suitable for comprises silicon-dioxide, magnesium chloride, aluminum oxide, polynite, clay etc.Wherein, magnesium chloride support is that current industrial application is maximum, the most effective carrier.But also there is following key issue in current carried metallocene catalyst: the actual negative carrying capacity of catalyzer is low, and effective ingredient runs off in a large number when wash-out; The active ingredients of load is low; Promotor consumption high (alkylaluminoxane/active metal atom mol ratio is 500); During for olefinic polymerization, polymer performance does not also have clear improvement.Zirconocene, two indenes zirconium even loads on magnesium chloride, and are added the organic crosslinking agents such as polyvalent alcohol by Chinese patent CN135877A in preparation, and preparation need use a large amount of MAO like this, and preparation process is loaded down with trivial details.Japanese Patent also discloses and by chemical bond, part or title complex is loaded on carrier, but the not easily a large amount of catalyzer of load.Therefore, in the urgent need to the novel carriers that exploitation load process is simple, with low cost, and then the supported olefin polymerization catalyst that processability is excellent.
Summary of the invention
In order to solve novel carriers at present simple, with low cost to exploitation load process and the excellent supported olefin polymerization catalyst of processability in the urgent need to, the invention provides a kind of triple phenoxyl bicyclic pentadiene titanium catalyst and preparation thereof and utilize it to carry out the method for olefinic polymerization catalysis reaction.
A kind of triple phenoxyl bicyclic pentadiene titanium catalyst, structural formula is as follows:
Wherein, R
1and R
2the substituting group on phenoxy group aromatic ring, both one of for H and another one is H, C
1~ C
4alkyl, C
1~ C
4alkoxyl group, C
1~ C
4alkyl silyl or phenyl in any one or both be all C
1~ C
4alkyl.
Described triple phenoxyl bicyclic pentadiene titanium catalyst is: poly-three (xenyl bis-tetramethyl cyclopentadienyltitanium base) triphen benzene three ether, poly-three (xenyl bis-tetramethyl cyclopentadienyltitanium base) triisopropyl replaces triphen benzene three ether, poly-three (xenyl bis-tetramethyl cyclopentadienyltitanium base) tri-tert replaces triphen benzene three ether, poly-three (xenyl bis-tetramethyl cyclopentadienyltitanium base) six sec.-propyl replace triphen benzene three ether, poly-three (xenyl bis-tetramethyl cyclopentadienyltitanium base) triphenyl replaces triphen benzene three ether, poly-three (xenyl bis-tetramethyl cyclopentadienyltitanium base) trimethyl silicon based replacement triphen benzene three ethers or poly-three (xenyl bis-tetramethyl cyclopentadienyltitanium base) trimethoxy replace triphen benzene three ether.
Its preparation method is as follows:
The benzenetriol salt of step one, synthesis of phenyl bridging
In ether, tetrahydrofuran (THF) or toluene kind solvent, by benzenetriol 2.8 ~ 3.2:1 stoichiometric reaction in molar ratio of strong alkaline substance and phenyl bridging, temperature of reaction Wei ?78 DEG C ~ 0 DEG C, the reaction times is 3 ~ 24 hours, reacts to carry out under protective atmosphere; Filtration extracts solvent; Described strong alkaline substance is basic metal, alkali alkyl, alkalimetal hydride or alkyl halide magnesium;
Step 2, synthesis triple phenoxyl bicyclic pentadiene titanium catalyst
In organic solvent, by the benzenetriol salt of xenyl bis-tetramethyl cyclopentadienyl titanous chloride and above-mentioned obtained phenyl bridging in molar ratio 1.4 ~ 1.6:1 react, temperature of reaction is 20 DEG C ~ 90 DEG C, reaction times is 8 ~ 36 hours, filter, gained solid is after organic solvent extraction, and removing organic solvent collects solid matter, i.e. triple phenoxyl bicyclic pentadiene titanium catalyst; Described organic solvent is toluene or ether.
Described strongly alkaline compound preferred alkyl lithium.
In the preparation of triple phenoxyl bicyclic pentadiene titanium catalyst, reaction formula is as follows:
Step one:
Step 2:
A purposes for triple phenoxyl bicyclic pentadiene titanium catalyst, the equal polyreaction of catalyzed alkene.
The concrete grammar of the equal polyreaction of catalyzed alkene is as follows:
With triple phenoxyl bicyclic pentadiene titanium catalyst for Primary Catalysts, take alkylaluminoxane as promotor, or with the co-catalyst system that organoboron compound and aluminum alkyls form, the equal polyreaction of catalyzed alkene; The temperature range of described polyreaction is 40 DEG C ~ 100 DEG C, polymerization pressure scope is 1 ~ 60 normal atmosphere, and reaction is carried out in organic solvent, organic solvent is any one in hexane, heptane, octane, hexanaphthene, methylcyclohexane, toluene, dimethylbenzene and mixed alkanes.When described alkylaluminoxane is methylaluminoxane, modified methylaluminoxane, ethylaluminoxane or isobutyl aluminium alkoxide, in promotor, in aluminium and Primary Catalysts, titanium is 100 ~ 1200:1 in molar ratio; Organic boride described in co catalysis system is Ph
3cB (C
6f
5)
4, B (C
6f
5)
3or R
4nB (C
6f
5)
4, and when described aluminum alkyls is trimethyl aluminium, triethyl aluminum or triisobutyl aluminium, in co-catalyst system, in boron, aluminium and Primary Catalysts, atoms metal is 1 ~ 10:1 ~ 500:1 in molar ratio.
Advantage of the present invention:
1, the present invention is from loaded catalyst, and compared with existing catalyzer, load process is simple;
2, catalyst activity of the present invention has higher catalytic activity compared to existing technology, therefore as the usage quantity that can greatly reduce promotor during Primary Catalysts, reduces and produces polyolefinic cost;
3, catalyzer of the present invention carries out the polyolefin molecular weight wider distribution that catalyzed alkene homopolymerization obtains.
Embodiment
Below in conjunction with embodiment detailed explanation and description technical scheme of the present invention.
The preparation of embodiment 1 triple phenoxyl bicyclic pentadiene titanium catalyst Ti1
At 0 DEG C, 0.50mmol triisopropyl is replaced triphen benzenetriol, i.e. R wherein
1substituting group is sec.-propyl, R
2substituting group is that the benzenetriol of the phenyl bridging of H is added to and is equipped with in the reaction ampulla of toluene solvant, and after stirring, add the butyllithium of 1.5mmol, react 3 hours, whole reaction process needs to carry out under nitrogen protection; Then, after temperature is raised to room temperature gradually, the xenyl bis-tetramethyl cyclopentadienyl titanous chloride adding 0.75mmol is heated to 80 DEG C, reacts 8 hours.The solvent in vacuo of reaction product is drained, washes rear filtration with toluene, obtain orange pressed powder.Productive rate is 58%.Results of elemental analyses is: C:65.61, H:7.24 (%).
The preparation of embodiment 2 triple phenoxyl bicyclic pentadiene titanium catalyst Ti1
At-78 DEG C, 0.50mmol triisopropyl is replaced triphen benzenetriol, and be added to and be equipped with in the reaction ampulla of toluene solvant, after stirring, add the butyllithium of 1.5mmol, react 24 hours, whole reaction process needs to carry out under nitrogen protection; Then, after temperature is raised to room temperature gradually, the xenyl bis-tetramethyl cyclopentadienyl titanous chloride adding 0.75mmol is heated to 50 DEG C, reacts 8 hours.The solvent in vacuo of reaction product is drained, washes rear filtration with toluene, obtain orange pressed powder.Productive rate is 45%.Results of elemental analyses is: C:65.51, H:7.19 (%).With the triple phenoxyl bicyclic pentadiene titanium catalyst Ti1 prepared by embodiment 1, there is identical structure.
The preparation of embodiment 3 triple phenoxyl bicyclic pentadiene titanium catalyst Ti2
At-20 DEG C, 0.50mmol tri-tert is replaced triphen benzenetriol, i.e. R wherein
1substituting group is the tertiary butyl, R
2substituting group is that the benzenetriol of the phenyl bridging of H is added to and is equipped with in the reaction ampulla of toluene solvant, after stirring, adds the butyllithium of 1.5mmol, and continue stirring 3 hours, whole reaction process needs to carry out under nitrogen protection; Then, after temperature is raised to room temperature gradually, the xenyl bis-tetramethyl cyclopentadienyl titanous chloride adding 0.75mmol is heated to 80 DEG C, reacts 8 hours.Drained by the solvent in vacuo of reaction product, wash rear filtration with toluene, obtain orange-red pressed powder, productive rate is 64%.Results of elemental analyses is: C:66.91, H:6.79 (%).
The preparation of embodiment 4 triple phenoxyl bicyclic pentadiene titanium catalyst Ti3
At 0 DEG C, 0.50mmol six sec.-propyl is replaced triphen benzenetriol, i.e. R wherein
1substituting group is sec.-propyl, R
2substituting group is that the benzenetriol of the phenyl bridging of sec.-propyl is added to and is equipped with in the reaction ampulla of toluene solvant, after stirring, adds the butyllithium of 1.5mmol, and continue stirring 3 hours, whole reaction process needs to carry out under nitrogen protection; Then, after temperature is raised to room temperature gradually, the xenyl bis-tetramethyl cyclopentadienyl titanous chloride adding 0.75mmol is heated to 80 DEG C, reacts 8 hours.Drained by the solvent in vacuo of reaction product, wash rear filtration with toluene, obtain orange pressed powder, productive rate is 65%.Results of elemental analyses is: C:67.99, H:7.11 (%).
The preparation of embodiment 5 triple phenoxyl bicyclic pentadiene titanium catalyst Ti4
At 0 DEG C, 0.50mmol triphenyl is replaced triphen benzenetriol, i.e. R wherein
1substituting group is phenyl, R
2substituting group is that the benzenetriol of the phenyl bridging of H is added to and is equipped with in the reaction ampulla of toluene solvant, after stirring, adds the butyllithium of 1.5mmol, and continue stirring 3 hours, whole reaction process needs to carry out under nitrogen protection; Then, after temperature is raised to room temperature gradually, the xenyl bis-tetramethyl cyclopentadienyl titanous chloride adding 0.75mmol is heated to 80 DEG C, reacts 8 hours.Drained by the solvent in vacuo of reaction product, wash rear filtration with toluene, obtain orange pressed powder, productive rate is 51%.Results of elemental analyses is: C:67.18, H:6.10 (%).
The preparation of embodiment 6 triple phenoxyl bicyclic pentadiene titanium catalyst Ti5
At 0 DEG C, by trimethyl silicon based for 0.50mmol replacement triphen benzenetriol, i.e. R wherein
1substituting group is trimethyl silicon based, R
2substituting group is that the benzenetriol of the phenyl bridging of H is added to and is equipped with in the reaction ampulla of toluene solvant, after stirring, adds the butyllithium of 1.5mmol, and continue stirring 3 hours, whole reaction process needs to carry out under nitrogen protection; Then, after temperature is raised to room temperature gradually, the xenyl bis-tetramethyl cyclopentadienyl titanous chloride adding 0.75mmol is heated to 80 DEG C, reacts 8 hours.Drained by the solvent in vacuo of reaction product, wash rear filtration with toluene, obtain orange-red pressed powder, productive rate is 58%.Results of elemental analyses is: C:61.75, H:7.21 (%).
The preparation of embodiment 7 triple phenoxyl bicyclic pentadiene titanium catalyst Ti6
At 0 DEG C, 0.50mmol trimethoxy is replaced triphen benzenetriol, i.e. R wherein
1substituting group is methoxyl group, R
2substituting group is that the benzenetriol of the phenyl bridging of H is added to and is equipped with in the reaction ampulla of toluene solvant, after stirring, adds the butyllithium of 1.5mmol, and continue stirring 3 hours, whole reaction process needs to carry out under nitrogen protection; Then, after temperature is raised to room temperature gradually, the xenyl bis-tetramethyl cyclopentadienyl titanous chloride adding 0.75mmol is heated to 80 DEG C, reacts 8 hours.Drained by the solvent in vacuo of reaction product, wash rear filtration with toluene, obtain orange-yellow pressed powder, productive rate is 49%.Results of elemental analyses is: C:62.30, H:6.37 (%).
The preparation of embodiment 8 triple phenoxyl bicyclic pentadiene titanium catalyst Ti7
At 0 DEG C, by 0.50mmol triphen benzenetriol, i.e. R wherein
1, R
2the benzenetriol that substituting group is the phenyl bridging of H is added to and is equipped with in the reaction ampulla of toluene solvant, after stirring, adds the butyllithium of 1.5mmol, and continue stirring 3 hours, whole reaction process needs to carry out under nitrogen protection; Then, after temperature is raised to room temperature gradually, the xenyl bis-tetramethyl cyclopentadienyl titanous chloride adding 0.75mmol is heated to 80 DEG C, reacts 8 hours.Drained by the solvent in vacuo of reaction product, wash rear filtration with toluene, obtain orange-yellow pressed powder, productive rate is 56%.Results of elemental analyses is: C:63.90, H:6.02 (%).
Embodiment 9
Butyllithium in above embodiment is changed to basic metal, alkali alkyl, alkalimetal hydride or alkyl halide magnesium, under condition same as the previously described embodiments, all can obtains the product of same nature.
Embodiment 10 is with Ph
3cB (C
6f
5)
4and i-Bu
3al is the equal polyreaction of co-catalyst system catalyzed ethylene
Be aggregated in 250mL autoclave and carry out, reactor under vacuo 140 DEG C insulation 2 hours after, under the ethene atmosphere of a standard atmospheric pressure, question response still is down to 40 DEG C ~ 100 DEG C, the toluene solution of 50mL is added in reactor, then, by feeder under ethene environment respectively by 5 μm of ol Primary Catalystss (i.e. Ti1, Ti2 and Ti3) and a certain amount of triisobutyl aluminium and Ph
3cB (C
6f
5)
4toluene mixed solution 10mL add in reactor, then ethylene pressure rises to 5 normal atmosphere, and starts timing.Generally when not special dated, the reaction times is generally 2 hours.Reaction terminates rear emptying reactor, stops polyreaction with 10%HCl/ ethanolic soln.Polymkeric substance after filtration, fully washs with water and ethanol, and 60 DEG C of vacuum-dryings are to constant weight.
Table 1
| Al∶Ti | B∶Ti | T(℃) | Polymer output (g) | Mw(×10 4) | Mw/Mn |
| 200 | 1.2 | 40 | 0.17 | 5.69 | 3.65 |
| 200 | 1.2 | 50 | 0.24 | 23.91 | 9.68 |
| 200 | 1.2 | 60 | 3.60 | 24.87 | 4.07 |
| 150 | 1.2 | 60 | 3.19 | 28.29 | 3.54 |
Table 1 is triphen benzenetriol bicyclic pentadiene titanium polymer (Ti1) replaced with single sec.-propyl is that catalyst ethylene homo closes reaction.
Table 2
| Numbering | Al∶Ti | B∶Ti | Temperature (DEG C) | Polymer output (g) | Mw(×10 4) | Mw/Mn |
| Ti2 | 200 | 1.2 | 50 | 0.21 | 12.33 | 4.14 |
| Ti2 | 200 | 1.2 | 60 | 1.34 | 14.64 | 7.19 |
| Ti3 | 200 | 1.2 | 40 | 0.24 | 6.15 | 5.10 |
| Ti3 | 200 | 1.2 | 50 | 0.27 | 7.46 | 4.47 |
| Ti3 | 200 | 1.2 | 60 | 2.38 | 9.72 | 3.37 |
Triphen benzenetriol bicyclic pentadiene titanium polymer (Ti2) that table 2 replaces with single tertiary butyl and triphen benzenetriol bicyclic pentadiene titanium polymer (Ti3) that two sec.-propyl replaces close reaction for catalyst ethylene homo.
In table 1 and table 2, Al: Ti, B: Ti is the ratio of corresponding amount of substance, unless otherwise indicated.
Embodiment 11 with methylaluminoxane MAO for the equal polyreaction of promotor catalyzed ethylene
Be aggregated in 250mL autoclave and carry out, reactor under vacuo 140 DEG C insulation 2 hours after, under the ethene atmosphere of a standard atmospheric pressure, question response still is down to 40 DEG C ~ 100 DEG C, the toluene solution of 50mL is added in reactor, then by feeder under ethene environment respectively by the toluene mixed solution of a certain amount of MAO (as shown in table 3) of 5 μm of ol Primary Catalystss (i.e. Ti1, Ti2 and Ti3) and 10mL, add in reactor, then ethylene pressure rises to 5 normal atmosphere, and starts timing.Generally when not special dated, the reaction times is generally 2 hours.Reaction terminates rear emptying reactor, stops polyreaction with 10%HCl/ ethanolic soln.Polymkeric substance after filtration, fully washs with water and ethanol, and 60 DEG C of vacuum-dryings are to constant weight.
Table 3
| Cat | MAO∶Ti | Temperature (DEG C) | Polymer product (g) | Mw(×10 4) | Mw/Mn |
| Ti1 | 500 | 60 | 1.40 | 19.25 | 9.91 |
| Ti2 | 500 | 60 | 1.00 | 9.58 | 8.74 |
| Ti3 | 500 | 60 | 1.09 | 6.91 | 5.46 |
Table 3 is be Primary Catalysts catalyzed ethylene homopolymerization with Ti1, Ti2, Ti3.In table 3, MAO: Ti is the ratio of corresponding amount of substance, unless otherwise indicated.
Claims (10)
1. a triple phenoxyl bicyclic pentadiene titanium catalyst, is characterized in that, its molecular structural formula is as follows:
Wherein, R
1and R
2the substituting group on phenoxy group aromatic ring, both one of for H and another one is H, C
1~ C
4alkyl, C
1~ C
4alkoxyl group, C
1~ C
4alkyl silyl or phenyl in any one or both be all C
1~ C
4alkyl.
2. triple phenoxyl bicyclic pentadiene titanium catalyst according to claim 1, it is characterized in that, described triple phenoxyl bicyclic pentadiene titanium catalyst is: poly-three (xenyl bis-tetramethyl cyclopentadienyltitanium base) triphen benzene three ether, poly-three (xenyl bis-tetramethyl cyclopentadienyltitanium base) triisopropyl replaces triphen benzene three ether, poly-three (xenyl bis-tetramethyl cyclopentadienyltitanium base) tri-tert replaces triphen benzene three ether, poly-three (xenyl bis-tetramethyl cyclopentadienyltitanium base) six sec.-propyl replace triphen benzene three ether, poly-three (xenyl bis-tetramethyl cyclopentadienyltitanium base) triphenyl replaces triphen benzene three ether, poly-three (xenyl bis-tetramethyl cyclopentadienyltitanium base) trimethyl silicon based replacement triphen benzene three ethers or poly-three (xenyl bis-tetramethyl cyclopentadienyltitanium base) trimethoxy replace triphen benzene three ether.
3. a preparation method for the triple phenoxyl bicyclic pentadiene titanium catalyst of claim 1, it is characterized in that, concrete steps are as follows:
The benzenetriol salt of step one, synthesis of phenyl bridging
In ether, tetrahydrofuran (THF) or toluene kind solvent, by benzenetriol 2.8 ~ 3.2:1 stoichiometric reaction in molar ratio of strong alkaline substance and phenyl bridging, temperature of reaction is-78 DEG C ~ 0 DEG C, and the reaction times is 3 ~ 24 hours, reacts and carries out under protective atmosphere; Filtration extracts solvent; Described strong alkaline substance is basic metal, alkali alkyl, alkalimetal hydride or alkyl halide magnesium;
Step 2, synthesis triple phenoxyl bicyclic pentadiene titanium catalyst
In organic solvent, by the benzenetriol salt of xenyl bis-tetramethyl cyclopentadienyl titanous chloride and above-mentioned obtained phenyl bridging in molar ratio 1.4 ~ 1.6:1 react, temperature of reaction is 20 DEG C ~ 90 DEG C, reaction times is 8 ~ 36 hours, filter, gained solid is after organic solvent extraction, and removing organic solvent collects solid matter, i.e. triple phenoxyl bicyclic pentadiene titanium catalyst; Described organic solvent is toluene or ether.
4. the preparation method of triple phenoxyl bicyclic pentadiene titanium catalyst according to claim 3, is characterized in that, described strong alkaline substance is lithium alkylide.
5. a purposes for the triple phenoxyl bicyclic pentadiene titanium catalyst of claim 1, the equal polyreaction of catalyzed alkene.
6. the purposes of triple phenoxyl bicyclic pentadiene titanium catalyst according to claim 5, it is characterized in that, the concrete grammar of the equal polyreaction of catalyzed alkene is as follows: with triple phenoxyl bicyclic pentadiene titanium catalyst for Primary Catalysts, take alkylaluminoxane as promotor, the equal polyreaction of catalyzed alkene; The temperature range of described polyreaction is 40 DEG C ~ 100 DEG C, polymerization pressure scope is 1 ~ 60 normal atmosphere, and reaction is carried out in organic solvent, organic solvent is any one in the mixture of hexane, heptane, octane, hexanaphthene, methylcyclohexane, toluene, dimethylbenzene and above alkane; In promotor, in aluminium and Primary Catalysts, titanium is 100 ~ 1200:1 in molar ratio.
7. the purposes of triple phenoxyl bicyclic pentadiene titanium catalyst according to claim 6, is characterized in that, described alkylaluminoxane is methylaluminoxane, modified methylaluminoxane, ethylaluminoxane or isobutyl aluminium alkoxide.
8. the purposes of triple phenoxyl bicyclic pentadiene titanium catalyst according to claim 5, it is characterized in that, the concrete grammar of the equal polyreaction of catalyzed alkene is as follows: with triple phenoxyl bicyclic pentadiene titanium catalyst for Primary Catalysts, with the co-catalyst system that organoboron compound and aluminum alkyls form, the equal polyreaction of catalyzed alkene; The temperature range of described olefinic polyreaction is 40 DEG C ~ 100 DEG C, polymerization pressure scope is 1 ~ 60 normal atmosphere, and reaction is carried out in organic solvent, organic solvent is any one in the mixture of hexane, heptane, octane, hexanaphthene, methylcyclohexane, toluene, dimethylbenzene and above alkane; In described co-catalyst system, in boron, aluminium and Primary Catalysts, atoms metal is 1 ~ 10:1 ~ 500:1 in molar ratio.
9. the purposes of triple phenoxyl bicyclic pentadiene titanium catalyst according to claim 8, it is characterized in that, described organic boride is Ph
3cB (C
6f
5)
4, B (C
6f
5)
3or R
4nB (C
6f
5)
4.
10. the purposes of triple phenoxyl bicyclic pentadiene titanium catalyst according to claim 8 or claim 9, it is characterized in that, described aluminum alkyls is trimethyl aluminium, triethyl aluminum or triisobutyl aluminium.
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