CN1315891C - Method of preparing nano-polyethylene fiber using TiCl4/MCM-41 catalytic system extrusion polymerization - Google Patents
Method of preparing nano-polyethylene fiber using TiCl4/MCM-41 catalytic system extrusion polymerization Download PDFInfo
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- CN1315891C CN1315891C CNB2005100508005A CN200510050800A CN1315891C CN 1315891 C CN1315891 C CN 1315891C CN B2005100508005 A CNB2005100508005 A CN B2005100508005A CN 200510050800 A CN200510050800 A CN 200510050800A CN 1315891 C CN1315891 C CN 1315891C
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Abstract
The present invention discloses a method for preparing nanometer polyethylene fibers by the extrusion and the polymerization of a TiCl4 /MCM-41 catalytic system. A carrier B is arranged in normal hexane, treated by triethyl aluminium under normal temperature and then washed by the normal hexane; TiCl4 dilute diluted by the normal hexane is added into a normal hexane suspension treated by the triethyl aluminium; the suspension is stirred under normal temperature and washed by the normal hexane after reaction; normal hexane solvent is removed by a vacuum method under the normal temperature to obtain supported catalysts for polymerization; the triethyl aluminium is used as a cocatalyst; under the existence of beta cyclodextrin, the obtained supported catalysts are used for extruding and polymerizing ethene to manufacture the nanometer polyethylene fibers with the diameters of 30 to 80 nm. the operating procedures are all carried out under the protection of high-purity nitrogen. The present invention has the advantages of no need of specific production equipment, simple technique, low cost and easy industrial production.
Description
Technical field
The present invention relates to a kind of employing TiCl
4/ MCM-41 catalytic system extrusion polymerization is equipped with the method for nano-polyethylene fiber.
Technical background
Along with the development of nanotechnology, nano material application in practice more and more widely.Nanofiber is because of it has big specific surface area, high intensity becomes a research focus.At present, common nanofiber preparation method has gel spinning, stretching method, method of electrostatic spinning etc., but these preparation methods need a series of specific processing unitss and complicated treating processes.
Aida etc. have reported and a kind of cyclopentadienyl titanium dichloride have been loaded on the mesoporous silicon fibre, with MAO is promotor, catalyzed ethylene polymerization has made the method for nano-polyethylene fiber under the high pressure of 1Mpa, because of its PE chain is a uncrimping chain, so this fiber has higher intensity, the preparation nano-polyethylene fiber that is found to be of this method opens up a new way.Usefulness MCM-41 load cyclopentadienyl titanium dichlorides such as ZhiBin Ye have made nano-polyethylene fiber under 20 atmospheric high pressure.
These two kinds of methods all need very high polymerization pressure in polymerization process, and will adopt the relatively costly metallocene catalyst of price, thereby have increased production cost.
Summary of the invention
The object of the present invention is to provide a kind of TiCl of using
4/ MCM-41 catalyst system prepares nano-polyethylene fiber through extruding polymerization, and it adopts mesopore molecular sieve MCM-41 load TiCl
4The Ziegler-Natta catalyst that preparation is classical prepares nano-polyethylene fiber by extruding polymerization with the loading type Z-N catalyzer of gained under normal pressure.
The technical solution used in the present invention is as follows:
At first prepare the loading type Ziegler-Natta catalyst, prepare the method for nano-polyethylene fiber with this catalyzer through extruding polymerization then, its step is as follows:
One, loading type Ziegler-Natta catalyst:
1) material is formed
Titanium compound A, A are TiCl
4
Carrier B, B is mesopore molecular sieve MCM-41;
2) preparation process
Carrier B is mixed according to weight ratio with normal hexane at 1: 25, and normal temperature was handled 1～3 hour with the dilution triethyl aluminum of 5 times of carrier B weight down, washed 3～5 times with normal hexane then; TiCl with the normal hexane dilution
4Join in the normal hexane suspension liquid of the carrier B that triethyl aluminum was handled, stirring reaction is 1～3 hour under the room temperature, washes 3～5 times with normal hexane; Adopt the method for vacuum to remove remaining normal hexane solvent, obtain the loaded catalyst that polymerization is used after the drying;
Two, the preparation for preparing nano-polyethylene fiber through extruding polymerization:
Under the normal pressure, with the triethyl aluminum is promotor, [Al]/[Ti] is 10～40, in the presence of the beta-cyclodextrin of loaded catalyst weight 15～40%, carry out the ethene extruding polymerization with the loaded catalyst that obtains, the polymerization temperature of ethene is 30～50 ℃, and polymerization time is 5～60 minutes, and the nano-polyethylene fiber diameter that makes is 30～80nm;
Above-mentioned operating process is all carried out under the protection of high purity nitrogen.
Carrier B in the loading type Ziegler-Natta catalyst preparation process is mesopore molecular sieve MCM-41, and its aperture is 2.9nm.
The present invention compares with background technology, and the beneficial effect that has is:
The present invention adopts the Z-N catalyzer, and preparation process is simple, cost is low.Under normal pressure, utilize the hydroxyl of beta-cyclodextrin to destroy MCM-41 surfactivity center, prepare nano-polyethylene fiber by extruding polymerization, the production of such nano-polyethylene fiber does not need specific production unit, technology is simple, cost is low, is easy to suitability for industrialized production.
Embodiment
Embodiment 1
Under nitrogen protection, 1 400 ℃ of MCM-41 that handled of gram (aperture is 2.9nm) are joined in the 40ml normal hexane, be the triethyl aluminum stirring reaction 1 hour at room temperature of 0.955mol/l with 8ml concentration, normal hexane is given a baby a bath on the third day after its birth inferior; The TiCl that adds 5ml
4Hexane solution (0.91mol/l) at room temperature reacted 2 hours, removed the normal hexane solvent with normal hexane washing three times, vacuum then, obtained the powdery solid catalyzer, and year titanium amount of this catalyzer is 1.34mmolTi/g.
Under 50 ℃ of conditions of normal pressure, with 4.6mg beta-cyclodextrin and 16.5mg TiCl
4/ MCM-41 catalyzer joins the 50ml normal hexane, behind the stirring reaction 2 minutes, feed ethylene gas and make it saturated, the triethyl aluminum ([Al]/[Ti]=20) that adds the 0.5ml dilution then, react after 30 minutes and stop with acidifying ethanol, product after filtration, washing, drying, obtain the nano-polyethylene fiber that diameter is 30～80nm.
Embodiment 2
With the prepared supported catalyst of embodiment 1, under 50 ℃ of conditions of normal pressure, carry out vinyl polymerization, 3.8mg beta-cyclodextrin and 23.9mg TiCl
4/ MCM-41 catalyzer, [Al]/[Ti]=20, the reaction times is 30 minutes, product after filtration, washing, drying, obtain the nano-polyethylene fiber that diameter is 30～80nm.
Embodiment 3
With the prepared supported catalyst of embodiment 1, under 30 ℃ of conditions of normal pressure, carry out vinyl polymerization, 4.3mg beta-cyclodextrin and 18.8mg TiCl
4/ MCM-41 catalyzer, [Al]/[Ti]=20, the reaction times is 30 minutes, product after filtration, washing, drying, obtain the nano-polyethylene fiber that diameter is 30～80nm.
Embodiment 4
With the prepared supported catalyst of embodiment 1, under 30 ℃ of conditions of normal pressure, carry out vinyl polymerization, 9.3mg beta-cyclodextrin and 25.1mg TiCl
4/ MCM-41 catalyzer, [Al]/[Ti]=20, the reaction times is 30 minutes, product after filtration, washing, drying, obtain the nano-polyethylene fiber that diameter is 30～80nm.
Claims (1)
1, uses TiCl
4/ MCM-41 catalytic system extrusion polymerization is equipped with the method for nano-polyethylene fiber, it is characterized in that at first preparing the loading type Ziegler-Natta catalyst, prepares the method for nano-polyethylene fiber with this catalyzer through extruding polymerization then, and its step is as follows:
One, loading type Ziegler-Natta catalyst:
1) material is formed
Titanium compound A, A are TiCl
4
Carrier B, B is mesopore molecular sieve MCM-41;
2) preparation process
Carrier B is mixed according to weight ratio with normal hexane at 1: 25, and normal temperature was handled 1～3 hour with the dilution triethyl aluminum of 5 times of carrier B weight down, washed 3～5 times with normal hexane then; TiCl with the normal hexane dilution
4Join in the normal hexane suspension liquid of the carrier B that triethyl aluminum was handled, stirring reaction is 1～3 hour under the room temperature, washes 3～5 times with normal hexane; Adopt the method for vacuum to remove remaining normal hexane solvent, obtain the loaded catalyst that polymerization is used after the drying;
Two, the preparation for preparing nano-polyethylene fiber through extruding polymerization:
Under the normal pressure, with the triethyl aluminum is promotor, [Al]/[Ti] is 10～40, in the presence of the beta-cyclodextrin of loaded catalyst weight 15～40%, carry out the ethene extruding polymerization with the loaded catalyst that obtains, the polymerization temperature of ethene is 30～50 ℃, and polymerization time is 5～60 minutes, and the nano-polyethylene fiber diameter that makes is 30～80nm;
Above-mentioned operating process is all carried out under the protection of high purity nitrogen;
Carrier B in the described loading type Ziegler-Natta catalyst preparation process is mesopore molecular sieve MCM-41, and its aperture is 2.9nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100508005A CN1315891C (en) | 2005-07-21 | 2005-07-21 | Method of preparing nano-polyethylene fiber using TiCl4/MCM-41 catalytic system extrusion polymerization |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100508005A CN1315891C (en) | 2005-07-21 | 2005-07-21 | Method of preparing nano-polyethylene fiber using TiCl4/MCM-41 catalytic system extrusion polymerization |
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| CN1718597A CN1718597A (en) | 2006-01-11 |
| CN1315891C true CN1315891C (en) | 2007-05-16 |
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| CNB2005100508005A Expired - Fee Related CN1315891C (en) | 2005-07-21 | 2005-07-21 | Method of preparing nano-polyethylene fiber using TiCl4/MCM-41 catalytic system extrusion polymerization |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0857734A1 (en) * | 1997-02-11 | 1998-08-12 | Fina Technology, Inc. | Process for producing stereospecific polymers |
| CN1563114A (en) * | 2004-03-22 | 2005-01-12 | 浙江大学 | Polyethylene catalyst and preparation method |
-
2005
- 2005-07-21 CN CNB2005100508005A patent/CN1315891C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0857734A1 (en) * | 1997-02-11 | 1998-08-12 | Fina Technology, Inc. | Process for producing stereospecific polymers |
| CN1563114A (en) * | 2004-03-22 | 2005-01-12 | 浙江大学 | Polyethylene catalyst and preparation method |
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