CN100554275C - A kind of method of synthesizing mono-metallocene compound - Google Patents
A kind of method of synthesizing mono-metallocene compound Download PDFInfo
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Abstract
The method of a kind of synthesizing mono-metallocene compound of the present invention belongs to technical field of catalytic chemistry.Synthetic method is to be raw material with IVB family metal halide, with 1: 1 in molar ratio ratio of cyclopentadiene part, under nitrogen atmosphere in hydrocarbon organic solvent stirring reaction, temperature of reaction is-80～200 ℃, reaction times is 0.5～96 hour, at last solution concentration is separated out to product.Synthetic method of the present invention is very simple, only needs part and metal halide raw material are gone on foot direct reaction in equimolar ratio one, need not add other any assistant agent or auxiliary agents; Selecting for use of the organic solvent that this reaction is required makes that reaction product is easy to separate, and solution concentration can need only be obtained product; Help the large-scale commercial production and the application of metallocene.
Description
Technical field
The invention belongs to technical field of catalytic chemistry, concrete, the present invention relates to a kind of synthetic method that is fit to do the mono-metallocene compound of catalyzer.
Background technology
In recent years, a large amount of facts is verified, and in field of olefin polymerisation, the monocyclopentadienes metallic compound more and more gets more and more people's extensive concerning.Especially single metallocene-titanium metal compound not only can also generate syndiotactic polystyrene by styrene catalyzed syndiotactic polymerization owing to the polymerization of ethene and propylene, and normality can reach more than 90% between the syndiotactic polystyrene of generation.Syndiotactic polystyrene has caused people's extensive concern because of the advantageous characteristic on its structure and the performance.The constrained geometry configuration metallocene catalyst as a kind of single metallocene catalyst of specific type especially since their constitutional features and catalytic performance paid attention to by people.The unique distinction of constrained geometry configuration metallocene catalyst is, the space opening characteristic of such catalyzer, and therefore, they can be applied to the polymerization of various types of olefins and the copolymerization of ethene or propylene and one or more end alkene.By changing the substituting group on the metallocene compound part, can change the catalytic performance of metallocene compound to polyreaction, as polymerization activity, the molecular weight of polymkeric substance and distribution thereof, co-monomer content etc.But can produce which type of effect for substituent change, its deterministic process still will be leaned on experience to a great extent.
1986, Ishihara at first reported CpTiCl
3/ MAO homogeneous phase metallocene catalysis system has synthesized normality between height at 60 ℃, the polystyrene of high crystalline.After this, a large amount of human and material resources are put in this polymkeric substance research boom, thereby have started the process of SPS large-scale commercial production.
Nineteen ninety Okuda synthesizes a kind of amino-contained side chain list cyclopentadiene titanium compound, is referred to as the constrained geometry configuration metallocene catalyst usually, the patent of invention that Dow in 1991 and Exxon company have applied for this class catalyzer in succession.These patents (U.S.Pat.No.5,026,798; 5,057,475 and Eur.Pat.App1.0 420 436 A1; 0 416 815A2; 0 418 044 A2) to the structure of such catalyzer with should be used as detailed description.Such catalyzer Heat stability is good, polymeric reaction temperature can reach 160 ℃.A principal character of this class catalyzer is that it has open catalytic active site, allows macromolecular alkene and ethylene random copolymerization, produces the multiple polyolefin products that commercial value is arranged.But contain unsettled Si-N key in such catalyzer, in Preparation of Catalyst or polymerization process, this key is subjected to the nucleophilic reagent attack easily and ruptures.In addition, although the industrialization of such catalyzer because of its synthetic yield is low, is promoted its big area and is restricted.
People such as Tobin J.Marks are at U.S.Pat.No.5, and 856,258 have reported dibenzyl titanium complex synthetic that replaces above-mentioned amino-contained side chain part with the Cp part that methylphenoxy is replaced, structure and olefinic polymerization.This catalyzer is for ethene, and propylene and cinnamic catalyzed polymerization all have higher activity.But they only synthesize a kind of dibenzyl titanium compound, attempt the not success of synthetic other derivative.
People such as female sea in 2003 contain metallocene dichloro title complex synthetic of phenoxy group side chain, structure and olefinic polymerization at organometallics.This catalyzer all has higher activity for the copolymerization of ethene and ethene and macromolecular alkene.
Recent two decades comes, and people have dropped into great amount of manpower and material resources on the structure of studying catalyzer and performance.A large amount of have high reactivity and stereoselective metallocene catalysts have been synthesized.People also study the synthetic method of catalyzer, and have developed a large amount of synthetic methods.For example, lithium salts method, alkyl null method, amido null method and Me
3SiCl null method etc.Although these synthetic methods are still continued to use at present, the step of these synthetic methods is many, and synthetic difficulty is big, and synthetic yield is lower, and cost is higher.This has limited the large-scale industrial application of metallocene greatly.
Summary of the invention
The invention provides a kind of method of synthetic metallocene compound newly.This method not only step is simple, and has improved the synthetic yield of catalyzer greatly.
Specifically, the structure expression that has of catalyzer of the present invention is as follows:
Wherein Cp is single the replacement or polysubstituted cyclopentadienyl group, and substituent R can be identical or different, is selected from hydrogen, alkyl, alkenyl, alkyl silyl, alkenyl silyl or silica-based alkyl group etc. respectively.M is the metal that can combine with cyclopentadienyl, preferred titanium, zirconium or hafnium.X is a halogen.One of them substituent R can develop into the heteroatoms of bridging, its structure such as figure below:
n＝0，1 m＝0，1，2
L is a heteroatoms, can be O, S, N or P, R
3Be the substituting group on the L, R when L is O or S
3Do not exist, and when L is N or P, R
3Be to be hydrogen, alkyl, alkenyl, alkyl silyl, alkenyl silyl, aromatic yl group or silica-based alkyl group etc.Z is an inflexible or the flexible bridge that connects Cp and heteroatoms L.Z can be the phenyl bridge that replaces, the silicon bridge of replacement or contain the C bridge of 1～3 C.R
2Be the one or more substituting groups on the Z, can be selected from hydrogen, alkyl, alkenyl, alkyl silyl, alkenyl silyl, aromatic yl group or silica-based alkyl group etc.Z and L can develop jointly becomes a substituting group generation mono-metallocene compound.This substituting group can be selected from hydrogen, alkyl, alkenyl, alkyl silyl, alkenyl silyl, aromatic yl group or silica-based alkyl group etc.
The mono-metallocene compound that the present invention comparatively preferably is fit to do catalyzer comprises: pentamethyl-cyclopentadienyl titanous chloride, tetramethyl--butyl-cyclopentadienyl titanous chloride, tetramethyl--cyclopentadienyl titanous chloride, [2,4-di-t-butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) the benzene oxidation] titanium dichloride, [the 2-tertiary butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) the benzene oxidation] titanium dichloride, [2-phenyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] titanium dichloride, [2-methyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) the benzene oxidation] titanium dichloride, dimethyl-silicon bridging tetramethyl-ring pentadienyl-TERTIARY BUTYL AMINE base titanium dichloride, [2, the 4--tertiary butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] zirconium dichloride, pentamethyl-cyclopentadienyl tri-chlorination zirconium etc.
Importance of the present invention is that described catalyzer can be synthetic with a kind of one step process of real meaning, and this method steps is as follows:
In organic solvent, IVB family metal halide and the part that sets each other off are reacted under suitable temperature, after the reaction regular hour, solution concentration is separated out to solid, collect solid and obtain catalyzer.
The method of concrete synthesizing mono-metallocene compound is, with IV B family metal halide is raw material, with 1: 1 in molar ratio ratio of cyclopentadiene part, under nitrogen atmosphere in hydrocarbon organic solvent stirring reaction, temperature of reaction is-80～200 ℃, reaction times is 0.5～96 hour, at last solution concentration is separated out to product.
The IVB family metal halide of being washed can be the halogenide of titanium or zirconium, preferred TiCl
4The cyclopentadiene part can be 2,4-di-t-butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenol or the 2-tertiary butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenol or 2-phenyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenol or 2-methyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenol or pentamethyl-cyclopentadiene or tetramethyl--butyl-cyclopentadiene or tetramethyl--ethyl-cyclopentadiene or tetramethyl--propyl group-cyclopentadiene or tetramethyl--cyclopentadiene or (uncle's fourth amino-dimethyl is silica-based)-tetramethyl--cyclopentadiene etc.Said hydrocarbon organic solvent is dimethylbenzene or toluene or methylene dichloride or chloroform or hexane or pentane or sherwood oil.
Preferred temperature of reaction is-20～150 ℃, and the preferred reaction times is 2～36 hours.
Most important significance of the present invention is that used synthetic method is very simple, only needs part and metal halide raw material are gone on foot direct reaction in equimolar ratio one, does not need to add other any assistant agent or auxiliary agents.Selecting for use of the organic solvent that this reaction is required makes that reaction product is easy to separate, and solution concentration can need only be obtained product.Because method is simple, without the assistant agent auxiliary agent, be easy to separate, reduce cost greatly, help the large-scale commercial production and the application of metallocene.
Embodiment
Further specify the present invention below by embodiment, but the present invention is not limited to this.
Embodiment 1
The preparation of [2,4-di-t-butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] titanium dichloride
Under nitrogen atmosphere and room temperature to containing 5mmolTiCl
4The 20mL toluene solution in drip equivalent 2, the 50mL toluene solution of 4-di-t-butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenol dropwises back 60 ℃ and stirred 4～12 hours.Filter concentrated solvent with G4 fritted sand funnel.Get straight product 2.09g, productive rate 94.3%.
1The HNMR interpretation of result:
＝1.347(s，9H，Ar-
tBu)，1.354(s，9H，Ar-
tBu)，＝2.038(s，6H，C
5Me
4)，＝2.416(s，6H，C
5Me
4)，＝7.116(d，1H，Ar)，＝7.334(d，1H，Ar)。
13The CNMR interpretation of result:
171.60 4146.872 145.718 143.594 134.824 130.136(
)28.876 123.399123.111(Cp.)?35.016 34.758 31.724 29.524(Ar-
t 
13.486 13.000(Cp-CH
3)
Embodiment 2
The preparation of [the 2-tertiary butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] titanium dichloride
Under nitrogen atmosphere and room temperature to containing 5mmolTiCl
4The 20mL dichloromethane solution in drip the 50mL dichloromethane solution of the equivalent 2-tertiary butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenol, dropwise the back stirred overnight at room temperature, promptly 8～20 hours.Filter concentrated solvent with G4 fritted sand funnel.Get straight product 1.73g, productive rate 89.4%.
1The HNMR interpretation of result:
＝1.354(s，9H，Ar-
tBu).，＝2.038(s，6H，C
5Me
4)，＝2.429(s，6H，C
5Me
4)，＝7.261(s，1H，Ar)，＝7.335(d，1H，Ar.).＝7.352(d，1H，Ar)。
13The CNMR interpretation of result:
173.930 145.800 143.175 136.277 130.366 126.673(
)129.218 126.535123.715(Cp) 34.88629.426(Ar-
t 13.480 13.057(Cp-CH
3)
Embodiment 3
The preparation of [2-phenyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] two titanium nitrides
Under nitrogen atmosphere and room temperature to containing 5mmolTiCl
4The 20mL toluene solution in drip the 50mL toluene solution of equivalent 2-phenyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenol, dropwise back 100 ℃ and stirred 2～10 hours down.Filter with G4 fritted sand funnel, remove and desolvate crude product CH
2Cl
2With the hexane recrystallization.Get straight product 1.74g, productive rate 85.5%.
1The HNMR interpretation of result:
＝2.113(s，6H，C
5Me
4)，＝2.444(s，6H，C
5Me
4)，＝7.243-7.640(m，8H，Ar)
13The CNMR interpretation of result:
171.972 145.854 142.675 136.44 1130.763 130.244 129.011 128.363 127.813126.608(
)129.260127.382124.227(Cp.)13.599 13.118(Cp-CH
3)
Embodiment 4
The preparation of [2-methyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] titanium dichloride
Under nitrogen atmosphere and room temperature to containing 5mmolTiCl
4The 20mL toluene solution in drip the 50mL toluene solution of equivalent 2-methyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenol, dropwise back 140 ℃ and stirred 8～16 hours down.Filter with G4 fritted sand funnel, concentrated solvent adds an amount of hexane recrystallization.Get straight product 1.13g, productive rate 65.5%.
1The HNMR interpretation of result:
＝2.177(s，3H，Ar-CH
3).，＝2.060(s，6H，C
5Me
4)，＝2.426(s，6H，C
5Me
4)，＝7.033-7.359(m，3H，Ar)。
13The CNMR interpretation of result:
173.665 145.950 143.164 139.085 131.217 130.553(
)128.008 126.200123.559(Cp.)13.523 13.114(Cp-CH
3.)15.305(Ar-CH
3)
Embodiment 5
The preparation of pentamethyl-cyclopentadienyl titanous chloride
Under nitrogen atmosphere and-20 ℃ to containing 5mmolTiCl
420mLCH
2Cl
2Drip the 50mL CH of equivalent pentamethyl-cyclopentadiene in the solution
2Cl
2Solution dropwises back 80 ℃ and stirred 6 hours down.Filter with G4 fritted sand funnel, concentrated solvent gets straight product 0.89g, productive rate 61.5%.
1The HNMR interpretation of result:
＝2.380(s，15H，Cp-CH
3)。
13The CNMR interpretation of result:
138.175(Cp.)14.701(Cp-CH
3)。
Embodiment 6
The preparation of tetramethyl--butyl-cyclopentadienyl titanous chloride
Under nitrogen atmosphere and room temperature to containing 5mmolTiCl
420mL CH
2Cl
2Drip equivalent tetramethyl--butyl-cyclopentadiene 50mL CH in the solution
2Cl
2Solution dropwises back 80 ℃ and stirred 10 hours down.Filter with G4 fritted sand funnel, concentrated solvent adds an amount of hexane recrystallization.Get straight product 0.96g, productive rate 57.9%.
1The HNMR interpretation of result:
＝0.941(t，3H，
nBu-Me).，＝1.379(m，4H，
nBu-CH
2)，＝2.379(s，12H，Cp-Me)，＝2.851(t，2H，
nBu-CH
2)。
13The CNMR interpretation of result:
142.479 138.358 137.656 32.345 29.414 23.034 14.640 14.151。
Embodiment 7
The preparation of tetramethyl--ethyl-cyclopentadienyl titanous chloride
Under nitrogen atmosphere and room temperature to containing 5mmolTiCl
4The 20mL toluene solution in drip equivalent tetramethyl--ethyl-cyclopentadiene 50mL toluene solution, dropwise back 110 ℃ and stirred 20 hours.Filter with G4 fritted sand funnel, concentrated solvent adds an amount of hexane recrystallization.Get straight product 0.84g, productive rate 55.5%.
1The HNMR interpretation of result:
＝1.09(t，3H，Et-CH
3)，＝2.38(s，12H，Cp-Me)，＝2.88(q，2H，Et-CH
2)。
Embodiment 8
The preparation of tetramethyl--propyl group-cyclopentadienyl titanous chloride
Under nitrogen atmosphere and 60 ℃ to containing 5mmolTiCl
4The 20mL toluene solution in drip equivalent tetramethyl--propyl group-cyclopentadiene 50mL toluene solution, dropwise back 140 ℃ and stirred 2 hours.Filter with G4 fritted sand funnel, concentrated solvent adds an amount of hexane recrystallization.Get straight product 0.87g, productive rate 54.7%.
1The HNMR interpretation of result:
＝0.62(t，3H，
nPr-CH
3)，＝1.03(m，2H，
nPr-CH
2)，＝1.90(s，6H，Cp-Me)，＝1.97(s，6H，Cp-Me)，＝2.61(t，2H，
nPr-CH
2)。
Embodiment 9
The preparation of tetramethyl--cyclopentadienyl titanous chloride
Under nitrogen atmosphere and room temperature to containing 5mmolTiCl
4The 20mL xylene solution in drip equivalent tetramethyl--cyclopentadiene 50mL xylene solution, dropwise back 150 ℃ and stirred 6 hours.Filter with G4 fritted sand funnel, concentrated solvent adds an amount of hexane recrystallization.Get straight product 0.74g, productive rate 53.8%.
1The HNMR interpretation of result:
＝2.356(s，6H，Cp-Me).，＝2.407(s，6H，Cp-Me)，＝6.656(s，1H，Cp)。
Embodiment 10
Dimethyl-silicon bridging tetramethyl-ring pentadienyl-TERTIARY BUTYL AMINE base titanium dichloride [Me
2
Si (C
5
Me
4
) (N
t
Bu)] TiCl
2
Preparation
Under nitrogen atmosphere and-78 ℃ to containing 5mmolTiCl
420mLCH
2Cl
2Drip equivalent (uncle's fourth amino-dimethyl is silica-based)-tetramethyl--cyclopentadiene [Me in the solution
2Si (C
5Me
4) (N
tBu)] H
250mL CH
2Cl
2Solution dropwised the back stirring at room 36 hours.Filter with G4 fritted sand funnel, concentrated solvent adds an amount of hexane recrystallization.Get straight product 1.49g, productive rate 80.9%.
1The HNMR interpretation of result:
＝2.177(s，3H，Ar-CH
3).，＝2.060(s，6H，C
5Me
4)，＝2.426(s，6H，C
5Me
4)，＝7.033-7.359(m，3H，Ar)。
13The CNMR interpretation of result:
173.665 145.950 143.164 139.085 131.217 130.553(
)128.008 126.200123.559(Cp.)13.523 13.114(Cp-CH
3.) 15.305(Ar-CH
3)
Embodiment 11
The preparation of pentamethyl-cyclopentadienyl tri-chlorination zirconium
Under nitrogen atmosphere and room temperature to containing 5mmolZrCl
4The 20mL toluene solution in drip the 50mL toluene solution of equivalent pentamethyl-cyclopentadiene, dropwise back 110 ℃ and stir down and spend the night.Filter with G4 fritted sand funnel, concentrated solvent distil straight product 1.0g, productive rate 60%.
1The HNMR interpretation of result:
＝1.826(s，15H，Cp-CH
3)。
13The CNMR interpretation of result:
125.530(Cp.)13.007(Cp-CH
3)。
Embodiment 12
The preparation of [2, the 4--tertiary butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenoxy group] zirconium nitride)
Under nitrogen atmosphere and cryosel bath condition to containing 2mmolZrCl
4The 20mL xylene solution in drip 2 of equivalent, the 30mL xylene solution of 4-di-t-butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenol stirs after one hour 150 ℃ and heated 24 hours.G4 fritted sand funnel filters, and removes and desolvates, and uses CH
2Cl
2With the hexane recrystallization.Get straight product 0.34g, productive rate 34.9%.
1The HNMR interpretation of result:
＝1.36(s，9H，Ar-
tBu)，1.40(s，9H，Ar-
tBu)，＝2.04(s，6H，C
5Me
4)，＝2.42(s，6H，C
5Me
4)，＝7.13(d，1H，Ar)，＝7.34(d，1H，Ar)。
Embodiment 13
About solvent
Change the solvent xylene among the embodiment 1～12 or toluene or methylene dichloride into chloroform or hexane or pentane or sherwood oil, effect is identical.
Claims (3)
1, a kind of method of synthesizing mono-metallocene compound, with IVB family metal halide is raw material, with 1: 1 in molar ratio ratio of cyclopentadiene part, under nitrogen atmosphere in hydrocarbon organic solvent stirring reaction, temperature of reaction is-80～200 ℃, reaction times is 0.5～72 hour, at last solution concentration is separated out to product; Said cyclopentadiene part is 2,4-di-t-butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenol, the 2-tertiary butyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenol, 2-phenyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenol, 2-methyl-6-(2,3,4,5-tetramethyl-ring pentadienyl) phenol, pentamethyl-cyclopentadiene, tetramethyl--butyl-cyclopentadiene, tetramethyl--ethyl-cyclopentadiene, tetramethyl--propyl group-cyclopentadiene, tetramethyl--cyclopentadiene or (uncle's fourth amino-dimethyl is silica-based)-tetramethyl--cyclopentadiene.
According to the method for the described a kind of synthesizing mono-metallocene compound of claim 1, it is characterized in that 2, said raw material is the halogenide of titanium or zirconium; Said hydrocarbon organic solvent is dimethylbenzene or toluene or methylene dichloride or chloroform or hexane or pentane or sherwood oil.
According to the method for claim 1 or 2 described a kind of synthesizing mono-metallocene compounds, it is characterized in that 3, said raw material is TiCl
4The temperature of stirring reaction is 20～150 ℃, and the reaction times is 2～36 hours.
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| CN110655538B (en) * | 2019-10-08 | 2021-08-31 | 吉林大学 | Mono-metallocene trivalent transition metal complex containing neutral benzyl heteroatom ligand and application thereof |
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Non-Patent Citations (4)
| Title |
|---|
| A novel phenolate "constrained geometry" catalystsystem....... You-Xian Chen, et al.Organometallics,Vol.16 No.26. 1997 |
| A novel phenolate"constrained geometry"catalystsystem.......You-Xian Chen,et al.Organometallics,Vol.16 No.26. 1997 * |
| Synthesis, Structures, and Catalytic Properties of....... Yuetao Zhang, et al.Organometallics,Vol.22 No.19. 2003 |
| Synthesis, Structures, and Catalytic Properties of.......Yuetao Zhang,et al.Organometallics,Vol.22 No.19. 2003 * |
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