CN1524885A - Process for preparing carried catalyst for metallocene - Google Patents
Process for preparing carried catalyst for metallocene Download PDFInfo
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- CN1524885A CN1524885A CNA031052983A CN03105298A CN1524885A CN 1524885 A CN1524885 A CN 1524885A CN A031052983 A CNA031052983 A CN A031052983A CN 03105298 A CN03105298 A CN 03105298A CN 1524885 A CN1524885 A CN 1524885A
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Abstract
The invention provides a process for synthesizing load type metallocene catalyst, wherein organic metallocene compound is premixed with alkyl aluminium, and water containing inorganic carrying agent is charged continuously, thus integrating the synthesis of alkyl aluminium oxygenalkyl and the load of metallocene compound, and realizing simple manufacturing process, high-usage of alkyl aluminium raw material, and good catalytic property in catalyzed olefin polymerization.
Description
Technical field
The present invention relates to a kind of preparation method of for olefines polymerization carried metallocene catalyst.
Background technology
The carrying method of metallocene catalyst is a lot, substantially can be summarized as two big classes: has reacted inorganic carrier, alkylaluminoxane, organo-metallic cyclopentadinyl compound three (1) in toluene solvant after, decompression extracts toluene in the suspension, perhaps filter out the toluene solution of unreacted organo-metallic cyclopentadinyl compound, behind the hexane wash several, decompressing and extracting gets fine catalyst, relevant patent has US 5719241, and EP 0128045, and EP 0206794, US 5087788, US 5548014, and US 4072735, JP-62-129303, US 5965677, and US 4897455.(2) with after aluminum alkyls and the moisture inorganic carrier effect, add the organo-metallic cyclopentadinyl compound again, after reaction finishes, necessarily handle, obtain fine catalyst.As: behind the mixture and water-containing column effect of trimethyl aluminium (TMA) and triethyl aluminum, add the reaction of organo-metallic cyclopentadinyl compound again in the method that US 4937217 describes,, obtain the exsiccant solid catalyst through necessarily handling; US 4912075, and US 4935937, and US 4937301 is disclosed to be that trimethyl aluminium adds the water-containing column effect, again with the reaction of organo-metallic cyclopentadinyl compound, the treated exsiccant loaded catalyst that obtains.
In above-mentioned two kinds of methods, the preparation flow of first method is too complicated, needs the alkylaluminoxane of a large amount of high prices simultaneously; Directly use aluminum alkyls in the second method, saved reinforced process comparatively loaded down with trivial details in the catalyst cupport process, reduced the synthesis step of alkylaluminoxane, the Preparation of catalysts process is simplified.But because the aluminum alkyls of remnants is volatile in the reaction system, in the process that adds the organo-metallic cyclopentadinyl compound, evaporable TMA easily combines with the organo-metallic cyclopentadinyl compound and produces thick material and blocking pipeline makes the reinforced process of organo-metallic cyclopentadinyl compound be difficult to carry out.
Summary of the invention
The present invention provides a kind of method of more simplifying for preparing carried metallocene catalyst on the basis of above-mentioned prior art.
Preparation method of the present invention mixes organo-metallic cyclopentadinyl compound and aluminum alkyls earlier, under the agitation condition moisture inorganic carrier is added continuously, control reaction temperature is at-40 ℃～150 ℃, be preferably-5 ℃～80 ℃, reaction finish after desolventize, filter, aftertreatments such as washing, decompressing and extracting obtain catalyst solid.
Not have " temperature runaway " phenomenon in reactor be good to the adding speed control of moisture inorganic carrier among the present invention.
Aluminum alkyls of the present invention is the trialkylaluminium that meets following formula:
AlR
3
Wherein, R is C
1～C
20Alkyl, be preferably methyl and isobutyl-.Aluminum alkyls can be the mixing solutions of single or two or more aluminum alkylss, and its concentration can be at 0.1～4molL
-1, be preferably 0.4～2.5molL
-1
Inorganic carrier can be silica gel, magnesium oxide, aluminum oxide, magnesium chloride etc., is preferably silica gel.
Organo-metallic cyclopentadinyl compound of the present invention can be any symmetrical structure or the unsymmetric structure that adopts general synthetic method to make, and the metallocene compound of bridging or non-bridging also can be the mixture of one or more cyclopentadinyl compounds.Enumerated the typical case's representative that is applicable to organo-metallic cyclopentadinyl compound of the present invention below:
Bis cyclopentadienyl zirconium dichloride (or titanium, hafnium),
Two indenyl zirconium dichlorides (or titanium, hafnium),
Two (butyl cyclopentadienyl) zirconium dichloride (or titanium, hafnium),
Two (tetramethyl-ring pentadienyl) zirconium dichloride (or titanium, hafnium),
(indenyl) (cyclopentadienyl) zirconium dichloride (or titanium, hafnium),
(fluorenyl) (cyclopentadienyl) zirconium dichloride (or titanium, hafnium),
Dimethyl-silicon (bridge) two indenyl zirconium dichlorides,
Methylene radical (bridge) indenyl (cyclopentadienyl) zirconium dichloride,
Dimethyl-silicon (bridge) cyclopentadienyl (TERTIARY BUTYL AMINE base) zirconium dichloride,
N-butyl cyclopentadienyl tri-chlorination zirconium (or titanium, hafnium),
Dicyclopentadienyl one hydrogen monochlor(in)ate zirconium (or titanium, hafnium).
Preparation method provided by the invention, because the organo-metallic cyclopentadinyl compound is to add before aluminum alkyls, thereby overcome in the organo-metallic cyclopentadinyl compound process problem of reinforced difficulty effectively, make the easier realization of operating process of preparation carried metallocene catalyst, simultaneously preparation time is further shortened.Adopt preparation method provided by the invention, the catalyzer that finally makes has good catalytic performance.
The following example can further strengthen the understanding of the present invention.
Embodiment
Embodiment 1
Reaction flask adds the 2g bis cyclopentadienyl zirconium dichloride after replacing through sufficient inertia, and adds 50ml1.3molL
-1The TMA toluene solution starts stirring, and steady temperature is at-5 ℃, under constantly stirring, 15g is added in the reaction flask gradually without the silica gel of dehydration, the reinforced back that finishes continues to stir 0.5 hour, be warming up to 50 ℃ and stirred 4 hours, removal of solvent under reduced pressure gets white loaded catalyst powder.
Get this this catalyzer 0.1 gram at 60 ℃, under the 0.8Mpa, made vinyl polymerization 1 hour, get 353 gram polyethylene.
Comparative Examples 1
Reaction flask adds 50ml1.3molL after replacing through sufficient inertia
-1The TMA toluene solution, start stirring, steady temperature is at-5 ℃, under constantly stirring, gradually add reaction flask in without the silica gel that dewaters 15g, the reinforced back that finishes continues to stir 0.5 hour, is warming up to 50 ℃ and stirs 4 hours, adds the 2g bis cyclopentadienyl zirconium dichloride, continue to stir 4 hours at 50 ℃, stopped reaction, removal of solvent under reduced pressure gets white loaded catalyst powder.
Get this this catalyzer 0.1 gram at 60 ℃, under the 0.8Mpa, made vinyl polymerization 1 hour, get 348 gram polyethylene.
Embodiment 2
Reaction flask adds 2.3g two (n-butyl cyclopentadienyl) zirconium dichloride after replacing through sufficient inertia, and adds 100ml1.5molL
-1The TMA toluene solution, start stirring, steady temperature is at-15 ℃, under constantly stirring, 15g is added in the reaction flask gradually without the silica gel of dehydration, the reinforced back that finishes continues to stir 0.5 hour, being warming up to 70 ℃ stirred 4 hours, the elimination solvent with hexane wash and removal of solvent under reduced pressure, gets white loaded catalyst powder.
Get this catalyzer 0.1 gram at 60 ℃, under the 0.8Mpa, made vinyl polymerization 1 hour, get 405 gram polyethylene.
Embodiment 3
Reaction flask adds 2.3g two (n-butyl cyclopentadienyl) zirconium dichloride after replacing through sufficient inertia, and adds 100ml1.3molL
-1TMA toluene solution and 30ml1.5molL
-1Triisobutylaluminum toluene solution, start stirring, steady temperature is at-15 ℃, under constantly stirring, 15g is added in the reaction flask gradually without the silica gel of dehydration, the reinforced back that finishes continues to stir 0.5 hour, being warming up to 50 ℃ stirred 4 hours, the elimination solvent with hexane wash and removal of solvent under reduced pressure, gets white loaded catalyst powder.
Get this catalyzer 0.1 gram at 60 ℃, under the 0.8Mpa, made vinyl polymerization 1 hour, get 426 gram polyethylene.
Embodiment 4
Reaction flask adds 1.95g (indenyl) (cyclopentadienyl) zirconium dichloride after replacing through sufficient inertia, and adds 100ml1.3molL
-1TMA toluene solution and 30ml1.5molL
-1Triisobutylaluminum toluene solution, start stirring, steady temperature is at-15 ℃, under constantly stirring, 15g is added in the reaction flask gradually without the silica gel of dehydration, the reinforced back that finishes continues to stir 0.5 hour, being warming up to 50 ℃ stirred 4 hours, the elimination solvent with hexane wash and removal of solvent under reduced pressure, gets white loaded catalyst powder.
Get this catalyzer 0.1 gram at 60 ℃, under the 0.8Mpa, made vinyl polymerization 1 hour, get 438 gram polyethylene.
Embodiment 5
Reaction flask adds 2.55g dimethyl-silicon (bridge) two indenyl zirconium dichlorides after replacing through sufficient inertia, and adds 100ml1.3molL
-1TMA toluene solution and 30ml1.5molL
-1Triisobutylaluminum toluene solution, start stirring, steady temperature under constantly stirring, gradually adds reaction flask in without the silica gel that dewaters 15g at-15 ℃, reinforced finishing, continue to stir 0.5 hour, be warming up to 50 ℃ and stirred the elimination solvent 4 hours, with hexane wash and removal of solvent under reduced pressure, get white loaded catalyst powder.
Get this catalyzer 0.1 gram at 60 ℃, under the 0.8Mpa, made vinyl polymerization 1 hour, get 429 gram polyethylene.
Embodiment 6
Reaction flask adds 2.0g methylene radical (bridge) indenyl (cyclopentadienyl) zirconium dichloride after replacing through sufficient inertia, and adds 100ml1.5molL
-1The toluene solution of triethyl aluminum, start stirring, steady temperature under constantly stirring, gradually adds reaction flask in without the silica gel that dewaters 15g at-15 ℃, reinforced finishing, continue to stir 0.5 hour, be warming up to 70 ℃ and stirred the elimination solvent 4 hours, with hexane wash and removal of solvent under reduced pressure, get white loaded catalyst powder.
Get this catalyzer 0.1 gram at 60 ℃, under the 0.8Mpa, made vinyl polymerization 1 hour, get 302 gram polyethylene.
Embodiment 7
Reaction flask adds 2.1g dimethyl-silicon (bridge) cyclopentadienyl (TERTIARY BUTYL AMINE base) zirconium dichloride after replacing through sufficient inertia, and adds 100ml1.5molL
-1The TMA toluene solution, start stirring, steady temperature under constantly stirring, gradually adds reaction flask in without the silica gel that dewaters 15g at-15 ℃, reinforced finishing, continue to stir 0.5 hour, be warming up to 70 ℃ and stirred the elimination solvent 4 hours, with hexane wash and removal of solvent under reduced pressure, get white loaded catalyst powder.
Get this catalyzer 0.1 gram at 60 ℃, under the 0.8Mpa, made vinyl polymerization 1 hour, get 445 gram polyethylene.
Embodiment 8
After reaction flask is replaced through sufficient inertia, add 1.44g n-butyl cyclopentadienyl tri-chlorination zirconium, and add 100ml1.5molL
-1The TMA toluene solution, start stirring, steady temperature under constantly stirring, gradually adds reaction flask in without the silica gel that dewaters 15g at-15 ℃, reinforced finishing, continue to stir 0.5 hour, be warming up to 70 ℃ and stirred the elimination solvent 4 hours, with hexane wash and removal of solvent under reduced pressure, get white loaded catalyst powder.
Get this catalyzer 0.1 gram at 60 ℃, under the 0.8Mpa, made vinyl polymerization 1 hour, get 372 gram polyethylene.
Claims (9)
1, a kind of preparation method of carried metallocene catalyst, it is characterized in that earlier organo-metallic cyclopentadinyl compound and aluminum alkyls being mixed, under the agitation condition moisture inorganic carrier is added continuously, control reaction temperature is at-40 ℃～150 ℃, reaction finish after desolventize, filter, aftertreatments such as washing, decompressing and extracting obtain catalyst solid.
2, preparation method according to claim 1 is characterized in that temperature of reaction is-5 ℃～80 ℃.
3, preparation method according to claim 1 is characterized in that the organo-metallic cyclopentadinyl compound can be symmetrical structure or unsymmetric structure, bridging or non-bridging.
4, preparation method according to claim 1 is characterized in that inorganic carrier can be silica gel, magnesium oxide, aluminum oxide, magnesium chloride.
5, preparation method according to claim 1 is characterized in that inorganic carrier is a silica gel.
6, the preparation method one of described according to claim 1 to 5 is characterized in that aluminum alkyls is the trialkylaluminium that meets following formula:
AlR
3
Wherein, R is C
1～C
20Alkyl.
7, preparation method according to claim 6 is characterized in that R is a methyl.
8, preparation method according to claim 6 is characterized in that R is an isobutyl-.
9, preparation method according to claim 6 is characterized in that aluminum alkyls can be the mixing solutions of one or more aluminum alkylss.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03105298 CN1221574C (en) | 2003-02-28 | 2003-02-28 | Process for preparing carried catalyst for metallocene |
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|---|---|---|---|
| CN 03105298 CN1221574C (en) | 2003-02-28 | 2003-02-28 | Process for preparing carried catalyst for metallocene |
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| CN1524885A true CN1524885A (en) | 2004-09-01 |
| CN1221574C CN1221574C (en) | 2005-10-05 |
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|---|---|---|---|
| CN 03105298 Expired - Fee Related CN1221574C (en) | 2003-02-28 | 2003-02-28 | Process for preparing carried catalyst for metallocene |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102286114A (en) * | 2010-06-21 | 2011-12-21 | 中国石油天然气股份有限公司 | Loading method of metallocene catalyst |
| CN101541839B (en) * | 2006-12-01 | 2012-12-12 | Lg化学株式会社 | Supported catalysts for olefin polymerization using transition metal compound having phenylene-bridge, method for preparing the same, and method for preparing polyolefin using the same |
| CN101580559B (en) * | 2008-05-14 | 2013-02-06 | Lg化学株式会社 | Preparation method of olefin polymers |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009107945A (en) * | 2007-10-26 | 2009-05-21 | Maruzen Pharmaceut Co Ltd | Inhibitor of optic nerve disorder and food and drink containing the same |
-
2003
- 2003-02-28 CN CN 03105298 patent/CN1221574C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101541839B (en) * | 2006-12-01 | 2012-12-12 | Lg化学株式会社 | Supported catalysts for olefin polymerization using transition metal compound having phenylene-bridge, method for preparing the same, and method for preparing polyolefin using the same |
| CN101580559B (en) * | 2008-05-14 | 2013-02-06 | Lg化学株式会社 | Preparation method of olefin polymers |
| US8946362B2 (en) | 2008-05-14 | 2015-02-03 | Lg Chem, Ltd. | Process for preparation of olefin polymers |
| CN102286114A (en) * | 2010-06-21 | 2011-12-21 | 中国石油天然气股份有限公司 | Loading method of metallocene catalyst |
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| CN1221574C (en) | 2005-10-05 |
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