CN104262411A - Synthesis method of metallocene compound (C5H5)2MCl2 - Google Patents

Synthesis method of metallocene compound (C5H5)2MCl2 Download PDF

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Publication number
CN104262411A
CN104262411A CN201410536472.9A CN201410536472A CN104262411A CN 104262411 A CN104262411 A CN 104262411A CN 201410536472 A CN201410536472 A CN 201410536472A CN 104262411 A CN104262411 A CN 104262411A
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mcl
metallocene compound
solution
solvent
synthetic method
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李洪伟
赫军
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YUEYANG KIMOUTAIN SCI-TECH Co Ltd
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YUEYANG KIMOUTAIN SCI-TECH Co Ltd
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Abstract

The invention provides a synthesis method of a metallocene compound (C5H5)2MCl2. The synthesis method comprises the steps as follows: a solvent solution containing C5H5Na is dropwise added into a solvent solution containing MCl4 for 30 min at the temperature of 0-30 DEG C in a protective gas atmosphere while the stirring is performed, and a mixed solution is obtained after the stirring is continuously performed for 1-2h; the mixed solution is filtered in the protective gas atmosphere to obtain filtrate and a residual part; and the filtrate is taken and used for preparing the solvent solution containing MCl4, the residual part is taken and subjected to separation and purification to obtain the metallocene compound (C5H5)2MCl2, and M is Ti, Zr or Hf. According to the synthesis method of the metallocene compound (C5H5)2MCl2, the mixed solution is filtered at first, and the residual part is subjected to separation and purification, so that the quantity of the solvents requiring reduced pressure distillation and removal is greatly reduced, and the energy consumption is reduced.

Description

Metallocene compound (C 5h 5) 2mCl 2synthetic method
  
Technical field
The present invention relates to metallocene compound, particularly relate to a kind of metallocene compound (C 5h 5) 2mCl 2synthetic method, wherein, M is Ti, Zr or Hf.
  
Background technology
Metallocene compound (C 5h 5) 2mCl 2(wherein, M is Ti, Zr or Hf) is important chemical industry supplementary material, mainly for the preparation of the catalyzer of olefinic polymerization, the hydrotreated lube base oil etc. containing C=C compound and superpolymer.The synthetic method of traditional metallocene compound has luxuriant sodium method and quadrol method, and luxuriant sodium method because of the thick product purity of synthesis higher, refining purifying technique is relatively simple and application is wider.But traditional luxuriant sodium method, be all adopt by solvent by heat vaporized recovery after luxuriant sodium solution and zirconium tetrachloride (titanium/hafnium) solution reaction generate bis cyclopentadienyl zirconium dichloride (titanium/hafnium), bis cyclopentadienyl zirconium dichloride (titanium/hafnium) solid residue after desolvation carries out refining operational path of purifying again.Because during synthesis bis cyclopentadienyl zirconium dichloride (titanium/hafnium), solvent usage quantity is comparatively large, higher in desolvation process energy consumption.
  
Summary of the invention
Based on this, be necessary for traditional luxuriant sodium method synthesis metallocene compound (C 5h 5) 2mCl 2the problem that in process, energy consumption is higher, provides the metallocene compound (C that a kind of energy consumption is low 5h 5) 2mCl 2synthetic method.
A kind of metallocene compound (C 5h 5) 2mCl 2synthetic method, comprise the following steps:
In protective gas atmosphere, at 0 DEG C ~ 30 DEG C, while stirring toward containing MCl 4solvent solution in drip containing C 5h 5the solvent solution of Na 30 minutes, continues stirring after 1 ~ 2 hour, obtains mixed solution; And
In protective gas atmosphere, described mixed solution is filtered, obtain filtrate and remainder; And
Get described filtrate described containing MCl for configuring 4solvent solution, get described remainder and carry out separating-purifying and obtain metallocene compound (C 5h 5) 2mCl 2, wherein, M is Ti, Zr or Hf.
Wherein in an embodiment, described protective gas is nitrogen.
Wherein in an embodiment, described MCl 4with C 5h 5the mol ratio of Na is 1:2.
Wherein in an embodiment, described containing MCl 4solvent solution in, MCl 4molar content be 0.5mol/L ~ 3mol/L.
Wherein in an embodiment, described containing C 5h 5c in the solvent solution of Na 5h 5the molar content of Na is 0.5mol/L ~ 3mol/L.
Wherein in an embodiment, described solvent is ether, toluene or tetrahydrofuran (THF).
Wherein in an embodiment, described in get described remainder and carry out separating-purifying and obtain metallocene compound (C 5h 5) 2mCl 2step in, the method of described separating-purifying is: at 30 DEG C ~ 60 DEG C,-0.05MPa, distillation is except desolventizing, obtaining solid materials, take trichloromethane as extraction agent, carries out extracting to described solid materials, obtain extracting solution, by concentrated for described extracting solution, cooling, filter, drying obtains described metallocene compound (C 5h 5) 2mCl 2.
Above-mentioned metallocene compound (C 5h 5) 2mCl 2synthetic method, first by mixed solution filter, remainder carries out separating-purifying, greatly reduces the quantity of solvent needing underpressure distillation to remove, reduces energy consumption.
In addition, mixed solution filters the filtrate that obtains and configures containing MCl for replacing solvent 4solvent solution, greatly reduce total consumption of solvent, energy-saving effect is obvious.
  
Embodiment
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail below to the specific embodiment of the present invention.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar improvement when intension of the present invention, therefore the present invention is by the restriction of following public concrete enforcement.
A kind of metallocene compound (C 5h 5) 2mCl 2synthetic method, comprise the following steps:
S110, in protective gas atmosphere, at 0 DEG C ~ 30 DEG C, while stirring toward containing MCl 4solvent solution in drip containing C 5h 5the solvent solution of Na 30 minutes, continues stirring after 1 ~ 2 hour, obtains mixed solution.
Wherein, M is Ti, Zr or Hf.I.e. MCl 4for TiCl 4, ZrCl 4or HfCl 4.
Protective gas is nitrogen.
Containing MCl 4solvent solution in MCl 4molar content be 0.5mol/L ~ 3mol/L.
Containing C 5h 5c in the solvent solution of Na 5h 5the molar content of Na is 0.5mol/L ~ 3mol/L.
Preferably, MCl 4with C 5h 5the mol ratio of Na is 1:2.
In the present embodiment, solvent is ether, toluene or tetrahydrofuran (THF).
Namely containing MCl 4solvent solution for containing MCl 4diethyl ether solution time, containing C 5h 5the solvent solution of Na is for containing C 5h 5the diethyl ether solution of Na.
Containing MCl 4solvent solution for containing MCl 4toluene solution time, containing C 5h 5the solvent solution of Na is for containing C 5h 5the toluene solution of Na.
Containing MCl 4solvent solution for containing MCl 4tetrahydrofuran solution time, containing C 5h 5the solvent solution of Na is for containing C 5h 5na's is tetrahydrofuran solution.
The reaction formula of step S110 is as follows:
MCl 4+2C 5H 5Na→(C 5H 5) 2MCl 2+2NaCl。
Wherein, containing C 5h 5the solvent solution of Na is obtained by following steps:
Under nitrogen protection; by sodium dimethylbenzene etc. not with heating and melting in the high boiling solvent of sodium generation chemical reaction, make sodium disperse to become fine particle to suspend in a solvent by stirring, then cooling makes sodium become solid granule-sodium sand; by sedimentation, filter and remove solvent, obtain sodium sand.
Above-mentioned sodium sand is dissolved in appropriate solvent (ether, toluene or tetrahydrofuran (THF)), stirs, control temperature, drip refining cyclopentadiene of purifying, obtain containing C 5h 5the solvent solution of Na.
S120, in protective gas atmosphere, above-mentioned mixed solution to be filtered, obtain filtrate and remainder.
Wherein, protective gas is nitrogen.
Above-mentioned mixed solution is with solvent, (C 5h 5) 2mCl 2, sodium-chlor etc. is main mixture, and is dissolved in the MCl in solvent containing a small amount of unreacted completely 4, wherein (C 5h 5) 2mCl 2part is solid crystal, and be partially soluble in solvent, sodium-chlor is mainly solid crystal.
S130, get above-mentioned filtrate for preparation containing MCl 4solvent solution, get above-mentioned remainder and carry out separating-purifying and obtain metallocene compound (C 5h 5) 2mCl 2, wherein, M is Ti, Zr or Hf.
Traditional luxuriant sodium method, preparation is containing MCl 4solvent solution in the usage quantity of solvent account for 40% ~ 50% of the total consumption of solvent in whole building-up process, and in present embodiment, adopt filtrate to be used for preparation containing MCl 4solvent solution, save a large amount of solvent, energy-saving effect is obvious.
Above-mentioned remainder of getting carries out separating-purifying and obtains metallocene compound (C 5h 5) 2mCl 2step in, the method of separating-purifying is: at 30 DEG C ~ 60 DEG C,-0.05MPa, distillation is except desolventizing, obtaining solid materials, take trichloromethane as extraction agent, carries out extracting to this solid materials, obtain extracting solution, by concentrated for this extracting solution, cooling, filter, drying obtains metallocene compound (C 5h 5) 2mCl 2.
In step S130, get remainder and carry out separating-purifying, greatly reduce the quantity of solvent needing underpressure distillation to remove, reduce energy consumption.
Be appreciated that in other embodiments, the method for separating-purifying is not limited to above method, as long as finally can obtain metallocene compound (C 5h 5) 2mCl 2.
Above-mentioned metallocene compound (C 5h 5) 2mCl 2synthetic method, compared to traditional luxuriant sodium method, yield improves 1% ~ 2%.
It is below specific embodiment.
Embodiment 1
Under nitrogen protection, at 0 DEG C, while stirring toward containing 0.2molTiCl 4tetrahydrofuran (THF) (300ml) solution in drip containing 0.4molC 5h 5tetrahydrofuran (THF) (350ml) solution of Na 30 minutes, continues stirring and obtains mixed solution after 2 hours.
Under nitrogen protection, above-mentioned mixed solution is filtered, obtain the remainder of 300ml filtrate and 350ml.
Get above-mentioned 300ml filtrate for prepare next time needed for reaction containing TiCl 4tetrahydrofuran solution.Get the remainder of 350ml, at 30 DEG C ,-0.05MPa, distillation removing tetrahydrofuran (THF), obtains solid materials, makes extraction agent with 150ml trichloromethane, extracting is carried out to this solid materials, obtains extracting solution, by concentrated for this extracting solution, cooling, filter, drying obtains metallocene compound (C 5h 5) 2tiCl 2.
After measured, metallocene compound (C 5h 5) 2tiCl 2boiling point be 269.1 DEG C, yield is 67%.
Comparative example 1
Under nitrogen protection, at 0 DEG C, while stirring toward containing 0.2molTiCl 4tetrahydrofuran (THF) (300ml) solution in drip containing 0.4molC 5h 5tetrahydrofuran (THF) (350ml) solution of Na 30 minutes, continues stirring and obtains mixed solution after 2 hours.
Get above-mentioned mixed solution 650ml, at 30 DEG C ,-0.05MPa, distillation removing tetrahydrofuran (THF), obtains solid materials, makes extraction agent with 150ml trichloromethane, extracting is carried out to this solid materials, obtains extracting solution, by concentrated for this extracting solution, cooling, filter, drying obtains metallocene compound (C 5h 5) 2tiCl 2.
After measured, metallocene compound (C 5h 5) 2tiCl 2boiling point be 269.1 DEG C, yield is 65%.
As can be seen from embodiment 1 and comparative example 1, the metallocene compound (C adopted in embodiment 1 5h 5) 2tiCl 2synthetic method, distillation removing quantity of solvent only have 350ml, and in comparative example 1 adopt metallocene compound (C 5h 5) 2tiCl 2synthetic method, the quantity of solvent of distillation removing is 650ml, the synthetic method adopting metallocene compound of the present invention is described, greatly reduces the quantity of solvent needing underpressure distillation to remove, and adopting the synthetic method of metallocene compound of the present invention, yield improves 2%.
Embodiment 2
Under nitrogen protection, at 30 DEG C, while stirring toward containing 0.2molZrCl 4tetrahydrofuran (THF) (300ml) solution in drip containing 0.4molC 5h 5tetrahydrofuran (THF) (350ml) solution of Na 30 minutes, continues stirring and obtains mixed solution after 2 hours.
Under nitrogen protection, above-mentioned mixed solution is filtered, obtain the remainder of 300ml filtrate and 350ml.
Get above-mentioned 300ml filtrate for prepare next time needed for reaction containing ZrCl 4tetrahydrofuran solution.Get the remainder of 350ml, at 60 DEG C ,-0.05MPa, distillation removing tetrahydrofuran (THF), obtains solid materials, makes extraction agent with 150ml trichloromethane, extracting is carried out to this solid materials, obtains extracting solution, by concentrated for this extracting solution, cooling, filter, drying obtains metallocene compound (C 5h 5) 2zrCl 2.
After measured, metallocene compound (C 5h 5) 2zrCl 2boiling point be 244.1 DEG C, yield is 65%.
Comparative example 2
Under nitrogen protection, at 30 DEG C, while stirring toward containing 0.2molZrCl 4tetrahydrofuran (THF) (300ml) solution in drip containing 0.4molC 5h 5tetrahydrofuran (THF) (350ml) solution of Na 30 minutes, continues stirring and obtains mixed solution after 2 hours.
Get above-mentioned mixed solution 650ml, at 60 DEG C ,-0.05MPa, distillation removing tetrahydrofuran (THF), obtains solid materials, makes extraction agent with 150ml trichloromethane, extracting is carried out to this solid materials, obtains extracting solution, by concentrated for this extracting solution, cooling, filter, drying obtains metallocene compound (C 5h 5) 2zrCl 2.
After measured, metallocene compound (C 5h 5) 2zrCl 2boiling point be 244.1 DEG C, yield is 64%.
As can be seen from embodiment 2 and comparative example 2, the metallocene compound (C adopted in embodiment 2 5h 5) 2zrCl 2synthetic method, distillation removing quantity of solvent only have 350ml, and in comparative example 2 adopt metallocene compound (C 5h 5) 2zrCl 2synthetic method, the quantity of solvent of distillation removing is 650ml, the synthetic method adopting metallocene compound of the present invention is described, greatly reduces the quantity of solvent needing underpressure distillation to remove, and adopting the synthetic method of metallocene compound of the present invention, yield improves 1%.
Embodiment 3
Under nitrogen protection, at 30 DEG C, while stirring toward containing 0.2molHfCl 4tetrahydrofuran (THF) (300ml) solution in drip containing 0.4molC 5h 5tetrahydrofuran (THF) (350ml) solution of Na 30 minutes, continues stirring and obtains mixed solution after 2 hours.
Under nitrogen protection, above-mentioned mixed solution is filtered, obtain the remainder of 300ml filtrate and 350ml.
Get above-mentioned 300ml filtrate for prepare next time needed for reaction containing HfCl 4tetrahydrofuran solution.Get the remainder of 350ml, at 60 DEG C ,-0.05MPa, distillation removing tetrahydrofuran (THF), obtains solid materials, makes extraction agent with 150ml trichloromethane, extracting is carried out to this solid materials, obtains extracting solution, by concentrated for this extracting solution, cooling, filter, drying obtains metallocene compound (C 5h 5) 2hfCl 2.
After measured, metallocene compound (C 5h 5) 2hfCl 2boiling point be 236.1 DEG C, yield is 59.8%.
Comparative example 3
Under nitrogen protection, at 30 DEG C, while stirring toward containing 0.2molHfCl 4tetrahydrofuran (THF) (300ml) solution in drip containing 0.4molC 5h 5tetrahydrofuran (THF) (350ml) solution of Na 30 minutes, continues stirring and obtains mixed solution after 2 hours.
Get above-mentioned mixed solution 650ml, at 60 DEG C ,-0.05MPa, distillation removing tetrahydrofuran (THF), obtains solid materials, makes extraction agent with 150ml trichloromethane, extracting is carried out to this solid materials, obtains extracting solution, by concentrated for this extracting solution, cooling, filter, drying obtains metallocene compound (C 5h 5) 2hfCl 2.
After measured, metallocene compound (C 5h 5) 2hfCl 2boiling point be 236.1 DEG C, yield is 59%.
Embodiment 4
Under nitrogen protection, at 20 DEG C, while stirring toward containing 0.3molHfCl 4ether (100ml) solution in drip containing 0.6molC 5h 5ether (200ml) solution of Na 30 minutes, continues stirring and obtains mixed solution after 1 hour.
Under nitrogen protection, above-mentioned mixed solution is filtered, obtain the remainder of 100ml filtrate and 200ml.
Get above-mentioned 100ml filtrate for prepare next time needed for reaction containing HfCl 4diethyl ether solution.Get the remainder of 200ml, at 50 DEG C ,-0.05MPa, distillation removing ether, obtains solid materials, makes extraction agent with 150ml trichloromethane, extracting is carried out to this solid materials, obtains extracting solution, by concentrated for this extracting solution, cooling, filter, drying obtains metallocene compound (C 5h 5) 2hfCl 2.
After measured, metallocene compound (C 5h 5) 2hfCl 2boiling point be 236.2 DEG C, yield is 58%.
Embodiment 5
Under nitrogen protection, at 25 DEG C, while stirring toward containing 0.1molTiCl 4toluene (200ml) solution in drip containing 0.2molC 5h 5toluene (400ml) solution of Na 30 minutes, continues stirring and obtains mixed solution after 1.5 hours.
Under nitrogen protection, above-mentioned mixed solution is filtered, obtain the remainder of 200ml filtrate and 400ml.
Get above-mentioned 200ml filtrate for prepare next time needed for reaction containing TiCl 4toluene solution.Get the remainder of 400ml, at 40 DEG C ,-0.05MPa, distillation removing toluene, obtains solid materials, makes extraction agent with 150ml trichloromethane, extracting is carried out to this solid materials, obtains extracting solution, by concentrated for this extracting solution, cooling, filter, drying obtains metallocene compound (C 5h 5) 2tiCl 2.
After measured, metallocene compound (C 5h 5) 2tiCl 2boiling point be 269.2 DEG C, yield is 66%.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.

Claims (7)

1. a metallocene compound (C 5h 5) 2mCl 2synthetic method, it is characterized in that, comprise the following steps:
In protective gas atmosphere, at 0 DEG C ~ 30 DEG C, while stirring toward containing MCl 4solvent solution in drip containing C 5h 5the solvent solution of Na 30 minutes, continues stirring after 1 ~ 2 hour, obtains mixed solution;
In protective gas atmosphere, described mixed solution is filtered, obtain filtrate and remainder; And
Get described filtrate described containing MCl for preparing 4solvent solution, get described remainder and carry out separating-purifying and obtain metallocene compound (C 5h 5) 2mCl 2, wherein, M is Ti, Zr or Hf.
2. metallocene compound (C according to claim 1 5h 5) 2mCl 2synthetic method, it is characterized in that, described protective gas is nitrogen.
3. metallocene compound (C according to claim 1 5h 5) 2mCl 2synthetic method, it is characterized in that, described MCl 4with C 5h 5the mol ratio of Na is 1:2.
4. metallocene compound (C according to claim 1 5h 5) 2mCl 2synthetic method, it is characterized in that, described containing MCl 4solvent solution in MCl 4molar content be 0.5mol/L ~ 3mol/L.
5. metallocene compound (C according to claim 1 5h 5) 2mCl 2synthetic method, it is characterized in that, described containing C 5h 5c in the solvent solution of Na 5h 5the molar content of Na is 0.5mol/L ~ 3mol/L.
6. metallocene compound (the C according to claim 1,4 or 5 5h 5) 2mCl 2synthetic method, it is characterized in that, described solvent is ether, toluene or tetrahydrofuran (THF).
7. metallocene compound (C according to claim 1 5h 5) 2mCl 2synthetic method, it is characterized in that, described in get described remainder and carry out separating-purifying and obtain metallocene compound (C 5h 5) 2mCl 2step in, the method of described separating-purifying is: at 30 DEG C ~ 60 DEG C,-0.05MPa, distillation is except desolventizing, obtaining solid materials, take trichloromethane as extraction agent, carries out extracting to described solid materials, obtain extracting solution, by concentrated for described extracting solution, cooling, filter, drying obtains described metallocene compound (C 5h 5) 2mCl 2.
CN201410536472.9A 2014-10-13 2014-10-13 Synthesis method of metallocene compound (C5H5)2MCl2 Pending CN104262411A (en)

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