CA2180981A1 - Use of gel-free alumoxane solution - Google Patents
Use of gel-free alumoxane solutionInfo
- Publication number
- CA2180981A1 CA2180981A1 CA002180981A CA2180981A CA2180981A1 CA 2180981 A1 CA2180981 A1 CA 2180981A1 CA 002180981 A CA002180981 A CA 002180981A CA 2180981 A CA2180981 A CA 2180981A CA 2180981 A1 CA2180981 A1 CA 2180981A1
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- Canada
- Prior art keywords
- alumoxane
- solution
- gel
- free
- supported catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
- C08F4/61912—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
- C08F4/61916—Component covered by group C08F4/60 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
- C08F4/6192—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Disclosed is a method of using gel-free alumoxane solution in the preparation of supported catalysts. These supported catalysts produce polymer particles with excellent morphology and minimal to no reactor fouling during polymerization.
Description
2~8098~
WO 95/18809 ~ PCT/US94/13367 TITLE: USE OF GEL-FREE ALUMOXANE SOLUTION
Field ofthe InYenti-~n~
4 This invention relates generally to polymerization catalysts and more particularly to the use of gel-free alumoxane solution as a cocatalyst for supported catalyst useful in the polymerization of olefins.
8 Back~round of the Invçntion . --Alumoxane solution has been known to be a usef~l cocatalyst with ml~t~ C-~nec in the formation of catalysts. A problem associated with alumoxane is the formation of gel or gel like particles. Problems associated with gelled 2 alumoxane include the gels plugging up reactor lines, enhancing fines or fine formation, creating difficulties in preparation of supported catalysts. US 5,157,137, ,UOI dl~d by reference, discloses a method for removing gels and providing clear gel-free solutions of alumoxane, and especially methylalumoxane by treating 6 the solution with certain alkali or alkaline earth metals ~r.mr~lln~lc US '137 discloses that the treatment results in alumoxane solutions that are stable and remain gel-free for extended periods of time.
The inventors have found that the use of gelled alumoxane can cause or contribute to fouling in a polymeri~ation reactor. Various supported catalyst techniques employing alumoxane solutions are l;nown. None appear to disclose or distinguish between the use of gelled versus gel-free alumoxane.
24 Summary of the Inventign -~
This invention relates to a method in wlIicll visually clear, 5llhstr~
transparent, gel-free alumoxane solution (AO) is used in the 1~ ~pal dLiu.~ of polyolefins comprising the step of removing gels from a gelled alumoxane solution, 28 or alternately separating gels from AO with gels and using the ' ' "y gel-free AO during the poly..,~ .a~ of olefins to polyolefins.
The invention further relates to a method for producing a supported catalyst comprising combining visually clear, c..~ 'ly gel-free alumoxane (AO) 32 obtained by separating gelled-AO from AO containing gelled particles with a dehydrated carrier and at least one Illei-''J~ to form a supported catalyst.
The invention further relates to a method for the pOlyll~ dLi~ of olefins to polyolefins combining contacting tl~e supported catalyst prepared as described 36 above with at least one olefin under suitable polymerization conditions, wherein the olefin contains from 2 to about 20 carbon atoms.
.. . . . . . ... . ..
wog5/1ssog i~ 98~ Pcr/uss4/l3367 The gel-free alumoxane is preferably methyl~l, ." ,vY ~ "~ employed in a ratio of aluminum in the alumoxane to transition metal in the "~c~n~ of about 12:1 to about 1000:1, preferably in a ratio of about 100:1 to about 500:1.
4 An alternate embodiment of this invention relates to a method to make a controlled particle size polyolefin comprising the steps of:
a. removing gels from a gelled alumoxane solution and combining the gel-free alumoxane solution with a dehydrated support and at least one 8 n.~t?lloc.~n~ to form a supported catalyst.
A further alternate ~-llbG''' ' relates to a method for preparing a supported catalyst comprisin~ of the steps of (a) acquiring a gelled alumoxane solution firom a vendor;
12 (b) removing gels from said alumoxane solution; and (c) combining the bub~ lly gel-free alumoxane solution of (b) with a support and a I "- to yield a supported catalyst.
A still further ~m~o-linn~n~ relates to a method for preparing a supported 6 system comprising the steps of (a) separating gels from a gelled AO solution to yield a ~u~a.lL;~ gel-free AO solution (b) combing the solution of (a) with a support and a I " - , said combining step occurring no more than seven days subsequent to the completion of step (a).
The invention is useful with any class of transition metal compounds or including mono, di, or tri cy~lv~ ..Lad;~ radical systems or 24 derivatives thereof Monocyclo-pentadienyl moieties include, for example, those as disclosed in US 4,808,561 or US 5,055~438 herein ;llcvl ,UUld~;;J by reference.
Carriers include organic or inorganic support mediums. Particularly preferred carriers include porous, inorganic mediums such as silica, alumina or 2~ silica alumina ~v~ ..1.;., -~ iv~ with silica being the most preferred.
Supported catalysts made with gel-free alumoxane solutions generally produce polymer having excellent morphology, controlled particle size, generally in granular form, with minimal to no fouling occuring in the reactor during polymerization.
DetailedDescriptionofPerferredE~ od;"~
US 4,808,561, US 5,240,894 and, US 4,921,825 disclose various methods of supporting transition metal ~vlll~Jvll~ or, ' " ~ employing alumoxane 36 as a cocatalyst. There are many pl~hli~:~ti~nc on the use of alumoxane as a ... . ..... , . .. _ _ WO 95/18809 218 ~ 9 8 ~ PCTNS94/~3367 cocatalyst in the ~ iull of supported catalysts. The references identified above are a ~ t~,. e~ e sample. While there are methûds reporting on producing gel-firee alumoxane, none appear to address the use of or advantages 4 firom using gel-firee alumoxane or ~ (MAO).
It is common practice in the art to shake up gelled solutions so as to uniformly distribute all particles. We have found that use of a uniformly distributed gelled alumoxane solution can yield a supported catalyst which produces 8 agglc,....,.dled polymer.
U.S. 5,157,137 discloses a method to avoid gels forming in an alumoxane solution. We have found that one can remove the gels and use the gel-free alumoxane solution without further treatment to produce a supported catalyst with 12 excellent p~,.ru~ relative to that produced with gelled alumoxane solutions.
The alkali treatment disclosed in US '137 is not necessary for use of the alumoxane solutions especially if the gel-free alumoxane is used immediately upon separation.
The alkali treatment disclosed in US '137 adds cost to the alumoxane. By 16 eliminating the treatment, a more cost efticient catalyst may be produced. The present invention describes a method of using alumoxane free of Ul--l~ -y additives or additional treatment steps. Since alumoxane will gel over time, it is preferred to use the separated gel-firee alumoxane within about 5-7 days after 20 separation, preferably about 3-5 days, and most preferably i~ ly upon separation to about 2 days for 10 wt.% alumoxane solutions. If employing 30wt.%
alumoxane it is generally advised to use the separated alumoxane within about 3-5 days, preferably about 1-3 days and most preferably immediately upon separation 24 to about I day.
The alumoxane solution may be purchased from a vendor, for example, Ethyl Corporation or Shering Corporation, or can be produced before use via known literature techniques.
28 The inventors have discovered that polymer particles with excellent ~ vl~Jllolu~y are produced from silica supported catalyst made from gel-free alumoxane. In addition, use of gel-free alumoxane solution in the ~ l dl;Oll of the catalyst results in minimal to no reactor fouling during the Pl.r ;~Liu 32 reaction. Still further, the use of gel-free alumoxane results in minimal to no polymer d~S~;lol~ L;ol~. A comparative example employing gelled alumoxane yielded a supported catalyst which produced fouling in the reactor and clumped polymer.
. .....
2~Q98~
US '561, US '82~ and US '894 each describe various methods of producing a supported cataiyst. A mr.~ifin~tion of the technique described in US '894 is the preferred ~ for the production of the supported catalyst. A preferred 4 _. I .o l; .. I for forming a supported catalyst comprises the steps of contacting a '1~ gel-free alumoxane solution, at least one " ~ ~, and a dehydrated carrier or support medium. The supported catalyst is optionally lc~ with alpha olefins. US '894 is silent on the use of gel-free 8 alumoxane. The present invention represents an ;,,~ u~ over that described in US '894.
ly gel-free~ is defined as a visually clear, substantially transparent alumoxane solution absent of haze and gels. In the alternative, gelled 12 alumoxane is defined as a translucent alumoxane solution containing haze and gels.
The color of the alumoxane solution is not releYant here provided the solution is bub~lallli~lly transparent, free of haze and gels. For purposes of this invention, one of skill in the art will appreciate that techniques for monitoring the gel particles 6 in the alumoxane solution, other than visual, will suffice. For example, alternative monitoring techniques including light beam 1. all~ m would be suitable for d~,~c...,;,.;.~g "gel-free" state of alumoxane. Once the alumoxane solution has become gelled or cloudy~ it is preferred to let the contents of the container settle.
A physical separation of the gel-free alumoxane from the gel like material may be achieved by conventional techniques such as physical withdrawal or by extractionby a syringe. The gel particles may be removed by filtration, separating the filtrate from the solution or be removed by other conventional liquid-solid separation 24 techniques such as c~ U~à~iOll and decanting the liquid.
I~ A ' ~1- _ I qJI c~c~Led by the general formula below may be employed with the gel-free alumoxane solution.
28 CpmMRnXq wherein Cp is a ~;yl IU~ I; ,yl ring or derivative thereof, M is a Group 4, ~i,or 6 transition metal, R is a hydrocarbyl group or hyllu~,albu~ group having from I to 32 20 carbon atoms, X is a halogen, and m=l -3, n=0-3, q=0-3, and the sum of m+n+q will be equal to the oxidation state of the transition metal. The, " may be bridged or unbridged, and include heteroatoms in the structure.
~WO95/18809 2l8ag8~ Pcrluss4ll3367 s Preferred .. , ~ are . ~ d by the general formula:
4 ~ gl~L
8 "2 }~I R6 ~7 t~SR9 2 (~ (~10~ 4 wherein: Ml is a metal of group 4, 5, or 6 ofthe Periodic Table, 6 Rl and R2 are identical or different, are one of a hydrogen atom, a Cl-CIo alkyl group, a Cl-CIo alkoxy group, a C6-CIo aryl group, a C6-CIo aryloxy group, a C2-C10 alkenyl group, a C7-C l0 aryla~ky~ group, a C7-C40 a~ky~ary~ group a C8-C40 ary~alkenyl group, or a halogen atom;
R3 and R~ are hydrogen atoms;
R5 and R6 are identical or different, preferably identical, are one of a halogen atom, a Cl-CIo alkyl group, which may be 1 - g ~, a C6-C10 aryl group, which may be '~ ~g. - -(1, a C2-CIo alkenyl group, a C7-C40 -arylalkyl 24 group, a C7-C40 alkylaryl group, a C8-C l0 arylalkenyl group, a -NR21s, -SR15, -ORI5, -oSiR315 or -PR21~ radical, wherein Rl5 is one of a halogen atom, a Cl-CI0 alkyl group, or a C6-CI0 aryl group;
R7 is Rll Rll Rll Rll Rll M2 _, _ Ml - M2 -, - M2 _ (CR213) - - O - M2 _ o _ Rll R
C -, - O - M2 _ ~ r' ~ f r~ 2~.80~81 WO 95/18~09 PCT/US94/13367 =BRII,=AIRll, -Ge-, -Sn-, -O-, -S-, = SO, =SO2, =NRII, =CO, PRII, or =p(O)RI l;
wherein:
4 Rl 1, R12 and Rl3 are identical or different and are a hydrogen atom, a halogen atom, a Cl-C20 alkyl group, a Cl-C20 fluoroalkyl group, a C6-C30 aryl group, a C6-C30 fluoroaryl group, a C l -C20 alkoxy group, a C2-C20 alkenyl group, a C7-C40 arylalkyl group, a C8-C40 arylalkenyl group, a C7-C40 alkylaryl group or 8 Rll and Rl2, a C7-C40 alkylaryl group, or Rl I and Rl3, together with the atoms binding them, can form ring systems;
M2 is silicon, germanium or tin~ or a derivative thereof;
R8 and R9 are identical or different and have the meanings as stated for 2 Rl l;
m and n are identical or different and are zero, I or 2, m plus n being zero, I or 2; and the radicals Rl are identical or different and have the meanings stated for 6 Rl 1, R12 and Rl3 or two adjacent Rl radicals can be joined together to form a ring system.
Examples of particularly preferred ~ Q~ or~ include rac-~ ' ' ' yll,is (2-methyl-4, 5-b~ o;~ .yl) -zirconium dichloride;
20 rac-d;ll~ l.rlailGIlJ;ylv;a (2-methylindenyl) -zirconium dichloride;
rac-.l;...~ll.yla;l~...l;yll,;s (2-methyl-4, 6-~' , u~.yl;,.~.".yl) -zirconium dichloride;
and rac-d;.l..,.h~ IV;a (2-methyl-4-phenylindenyl) -zirconium dichloride.
Exemplary ~ include illV~.O.,y~ !o~ i; ,yl titanocenes such as 24 ~ y. .1~ Alii ,.yl titanium trichloride, and the like, dimethylsilyl(tcll...r.~ .,y,,lu~ iPnyl)(t-butylamido)zirconium dimethyl (or dichloride) and the like, I,;s~y 1~ I; IYI L;ll,UIIOCC~..,.~ such as l~;a~,y~ I;r ~ ~YILh ~U~ IIII dichloride and the like.
28 In accordance with the preferred PmhorlimPnt for forming the supported catalyst, the support is dehydrated preferably at about 800C for about 18-24 hours or until a 1% or less loss on ignition value is obtained. Prior to use, the supported catalyst is dried to remove essentially all of the residual solvent which may be32 trapped in the pores of the carrier. This results in a free-flowing supported catalyst.
Once the supported catalyst is formed, it may be employed under various pol~ ,. i~l;u~ conditions. Suitable pGI ~ iOII conditions include gas phase, 36 or slurry pGlr.--~,.;~Ll;~nl. In a preferred PmhotlimPnt the supported catalyst ..... ... .. .. , . . . _ _ 2?8 WO 9~/18809 8 ~ PCT/US94/13367 prepared as described herein is contacted with alpha o~efins in a slurry pOIy~ .iL~lLioll reactor.
The invention is further illustrated by the following non limiting examples.
All ~,.,. i....,..l~ were carried out in nitrogen purged dry boxes. All solvents were purchased from ~011~11.~,. i.,~,l sources and were nitrogen purged or 8 distilled and dried over activated molecular sieves. Aluminum alkys were purchased as 20-25 wt% solutions from commercial sources. The MAO was purchased as 30 wt% in toluene from Shering Ul:)l ,UI)I d~iO~.
The polyll..,~;LdL;Ol\ procedure is as follows. In a clean, dry two liter 2 autoclave which had been flushed with propylene vapor, triethylaluminum, TEAL, (about 0.8 ml, about 1.5 M in heptane) was added and then the reactor closed andfilled with about 750 ml liquid propylene. With the reactor Iclll~ alul ~: at about 30"C the catalyst (as a 25 wt% oil slurry) was washed in via an addition tube with 16 about 250 ml propylene. The reactor was rapidly heated to about 65C. Afterthirty minutes the reactor was cooled and the excess propylene vented. The polymer was removed and dried.
Polymer analysis was carried out as described in US 5,026,798 and US
WO 95/18809 ~ PCT/US94/13367 TITLE: USE OF GEL-FREE ALUMOXANE SOLUTION
Field ofthe InYenti-~n~
4 This invention relates generally to polymerization catalysts and more particularly to the use of gel-free alumoxane solution as a cocatalyst for supported catalyst useful in the polymerization of olefins.
8 Back~round of the Invçntion . --Alumoxane solution has been known to be a usef~l cocatalyst with ml~t~ C-~nec in the formation of catalysts. A problem associated with alumoxane is the formation of gel or gel like particles. Problems associated with gelled 2 alumoxane include the gels plugging up reactor lines, enhancing fines or fine formation, creating difficulties in preparation of supported catalysts. US 5,157,137, ,UOI dl~d by reference, discloses a method for removing gels and providing clear gel-free solutions of alumoxane, and especially methylalumoxane by treating 6 the solution with certain alkali or alkaline earth metals ~r.mr~lln~lc US '137 discloses that the treatment results in alumoxane solutions that are stable and remain gel-free for extended periods of time.
The inventors have found that the use of gelled alumoxane can cause or contribute to fouling in a polymeri~ation reactor. Various supported catalyst techniques employing alumoxane solutions are l;nown. None appear to disclose or distinguish between the use of gelled versus gel-free alumoxane.
24 Summary of the Inventign -~
This invention relates to a method in wlIicll visually clear, 5llhstr~
transparent, gel-free alumoxane solution (AO) is used in the 1~ ~pal dLiu.~ of polyolefins comprising the step of removing gels from a gelled alumoxane solution, 28 or alternately separating gels from AO with gels and using the ' ' "y gel-free AO during the poly..,~ .a~ of olefins to polyolefins.
The invention further relates to a method for producing a supported catalyst comprising combining visually clear, c..~ 'ly gel-free alumoxane (AO) 32 obtained by separating gelled-AO from AO containing gelled particles with a dehydrated carrier and at least one Illei-''J~ to form a supported catalyst.
The invention further relates to a method for the pOlyll~ dLi~ of olefins to polyolefins combining contacting tl~e supported catalyst prepared as described 36 above with at least one olefin under suitable polymerization conditions, wherein the olefin contains from 2 to about 20 carbon atoms.
.. . . . . . ... . ..
wog5/1ssog i~ 98~ Pcr/uss4/l3367 The gel-free alumoxane is preferably methyl~l, ." ,vY ~ "~ employed in a ratio of aluminum in the alumoxane to transition metal in the "~c~n~ of about 12:1 to about 1000:1, preferably in a ratio of about 100:1 to about 500:1.
4 An alternate embodiment of this invention relates to a method to make a controlled particle size polyolefin comprising the steps of:
a. removing gels from a gelled alumoxane solution and combining the gel-free alumoxane solution with a dehydrated support and at least one 8 n.~t?lloc.~n~ to form a supported catalyst.
A further alternate ~-llbG''' ' relates to a method for preparing a supported catalyst comprisin~ of the steps of (a) acquiring a gelled alumoxane solution firom a vendor;
12 (b) removing gels from said alumoxane solution; and (c) combining the bub~ lly gel-free alumoxane solution of (b) with a support and a I "- to yield a supported catalyst.
A still further ~m~o-linn~n~ relates to a method for preparing a supported 6 system comprising the steps of (a) separating gels from a gelled AO solution to yield a ~u~a.lL;~ gel-free AO solution (b) combing the solution of (a) with a support and a I " - , said combining step occurring no more than seven days subsequent to the completion of step (a).
The invention is useful with any class of transition metal compounds or including mono, di, or tri cy~lv~ ..Lad;~ radical systems or 24 derivatives thereof Monocyclo-pentadienyl moieties include, for example, those as disclosed in US 4,808,561 or US 5,055~438 herein ;llcvl ,UUld~;;J by reference.
Carriers include organic or inorganic support mediums. Particularly preferred carriers include porous, inorganic mediums such as silica, alumina or 2~ silica alumina ~v~ ..1.;., -~ iv~ with silica being the most preferred.
Supported catalysts made with gel-free alumoxane solutions generally produce polymer having excellent morphology, controlled particle size, generally in granular form, with minimal to no fouling occuring in the reactor during polymerization.
DetailedDescriptionofPerferredE~ od;"~
US 4,808,561, US 5,240,894 and, US 4,921,825 disclose various methods of supporting transition metal ~vlll~Jvll~ or, ' " ~ employing alumoxane 36 as a cocatalyst. There are many pl~hli~:~ti~nc on the use of alumoxane as a ... . ..... , . .. _ _ WO 95/18809 218 ~ 9 8 ~ PCTNS94/~3367 cocatalyst in the ~ iull of supported catalysts. The references identified above are a ~ t~,. e~ e sample. While there are methûds reporting on producing gel-firee alumoxane, none appear to address the use of or advantages 4 firom using gel-firee alumoxane or ~ (MAO).
It is common practice in the art to shake up gelled solutions so as to uniformly distribute all particles. We have found that use of a uniformly distributed gelled alumoxane solution can yield a supported catalyst which produces 8 agglc,....,.dled polymer.
U.S. 5,157,137 discloses a method to avoid gels forming in an alumoxane solution. We have found that one can remove the gels and use the gel-free alumoxane solution without further treatment to produce a supported catalyst with 12 excellent p~,.ru~ relative to that produced with gelled alumoxane solutions.
The alkali treatment disclosed in US '137 is not necessary for use of the alumoxane solutions especially if the gel-free alumoxane is used immediately upon separation.
The alkali treatment disclosed in US '137 adds cost to the alumoxane. By 16 eliminating the treatment, a more cost efticient catalyst may be produced. The present invention describes a method of using alumoxane free of Ul--l~ -y additives or additional treatment steps. Since alumoxane will gel over time, it is preferred to use the separated gel-firee alumoxane within about 5-7 days after 20 separation, preferably about 3-5 days, and most preferably i~ ly upon separation to about 2 days for 10 wt.% alumoxane solutions. If employing 30wt.%
alumoxane it is generally advised to use the separated alumoxane within about 3-5 days, preferably about 1-3 days and most preferably immediately upon separation 24 to about I day.
The alumoxane solution may be purchased from a vendor, for example, Ethyl Corporation or Shering Corporation, or can be produced before use via known literature techniques.
28 The inventors have discovered that polymer particles with excellent ~ vl~Jllolu~y are produced from silica supported catalyst made from gel-free alumoxane. In addition, use of gel-free alumoxane solution in the ~ l dl;Oll of the catalyst results in minimal to no reactor fouling during the Pl.r ;~Liu 32 reaction. Still further, the use of gel-free alumoxane results in minimal to no polymer d~S~;lol~ L;ol~. A comparative example employing gelled alumoxane yielded a supported catalyst which produced fouling in the reactor and clumped polymer.
. .....
2~Q98~
US '561, US '82~ and US '894 each describe various methods of producing a supported cataiyst. A mr.~ifin~tion of the technique described in US '894 is the preferred ~ for the production of the supported catalyst. A preferred 4 _. I .o l; .. I for forming a supported catalyst comprises the steps of contacting a '1~ gel-free alumoxane solution, at least one " ~ ~, and a dehydrated carrier or support medium. The supported catalyst is optionally lc~ with alpha olefins. US '894 is silent on the use of gel-free 8 alumoxane. The present invention represents an ;,,~ u~ over that described in US '894.
ly gel-free~ is defined as a visually clear, substantially transparent alumoxane solution absent of haze and gels. In the alternative, gelled 12 alumoxane is defined as a translucent alumoxane solution containing haze and gels.
The color of the alumoxane solution is not releYant here provided the solution is bub~lallli~lly transparent, free of haze and gels. For purposes of this invention, one of skill in the art will appreciate that techniques for monitoring the gel particles 6 in the alumoxane solution, other than visual, will suffice. For example, alternative monitoring techniques including light beam 1. all~ m would be suitable for d~,~c...,;,.;.~g "gel-free" state of alumoxane. Once the alumoxane solution has become gelled or cloudy~ it is preferred to let the contents of the container settle.
A physical separation of the gel-free alumoxane from the gel like material may be achieved by conventional techniques such as physical withdrawal or by extractionby a syringe. The gel particles may be removed by filtration, separating the filtrate from the solution or be removed by other conventional liquid-solid separation 24 techniques such as c~ U~à~iOll and decanting the liquid.
I~ A ' ~1- _ I qJI c~c~Led by the general formula below may be employed with the gel-free alumoxane solution.
28 CpmMRnXq wherein Cp is a ~;yl IU~ I; ,yl ring or derivative thereof, M is a Group 4, ~i,or 6 transition metal, R is a hydrocarbyl group or hyllu~,albu~ group having from I to 32 20 carbon atoms, X is a halogen, and m=l -3, n=0-3, q=0-3, and the sum of m+n+q will be equal to the oxidation state of the transition metal. The, " may be bridged or unbridged, and include heteroatoms in the structure.
~WO95/18809 2l8ag8~ Pcrluss4ll3367 s Preferred .. , ~ are . ~ d by the general formula:
4 ~ gl~L
8 "2 }~I R6 ~7 t~SR9 2 (~ (~10~ 4 wherein: Ml is a metal of group 4, 5, or 6 ofthe Periodic Table, 6 Rl and R2 are identical or different, are one of a hydrogen atom, a Cl-CIo alkyl group, a Cl-CIo alkoxy group, a C6-CIo aryl group, a C6-CIo aryloxy group, a C2-C10 alkenyl group, a C7-C l0 aryla~ky~ group, a C7-C40 a~ky~ary~ group a C8-C40 ary~alkenyl group, or a halogen atom;
R3 and R~ are hydrogen atoms;
R5 and R6 are identical or different, preferably identical, are one of a halogen atom, a Cl-CIo alkyl group, which may be 1 - g ~, a C6-C10 aryl group, which may be '~ ~g. - -(1, a C2-CIo alkenyl group, a C7-C40 -arylalkyl 24 group, a C7-C40 alkylaryl group, a C8-C l0 arylalkenyl group, a -NR21s, -SR15, -ORI5, -oSiR315 or -PR21~ radical, wherein Rl5 is one of a halogen atom, a Cl-CI0 alkyl group, or a C6-CI0 aryl group;
R7 is Rll Rll Rll Rll Rll M2 _, _ Ml - M2 -, - M2 _ (CR213) - - O - M2 _ o _ Rll R
C -, - O - M2 _ ~ r' ~ f r~ 2~.80~81 WO 95/18~09 PCT/US94/13367 =BRII,=AIRll, -Ge-, -Sn-, -O-, -S-, = SO, =SO2, =NRII, =CO, PRII, or =p(O)RI l;
wherein:
4 Rl 1, R12 and Rl3 are identical or different and are a hydrogen atom, a halogen atom, a Cl-C20 alkyl group, a Cl-C20 fluoroalkyl group, a C6-C30 aryl group, a C6-C30 fluoroaryl group, a C l -C20 alkoxy group, a C2-C20 alkenyl group, a C7-C40 arylalkyl group, a C8-C40 arylalkenyl group, a C7-C40 alkylaryl group or 8 Rll and Rl2, a C7-C40 alkylaryl group, or Rl I and Rl3, together with the atoms binding them, can form ring systems;
M2 is silicon, germanium or tin~ or a derivative thereof;
R8 and R9 are identical or different and have the meanings as stated for 2 Rl l;
m and n are identical or different and are zero, I or 2, m plus n being zero, I or 2; and the radicals Rl are identical or different and have the meanings stated for 6 Rl 1, R12 and Rl3 or two adjacent Rl radicals can be joined together to form a ring system.
Examples of particularly preferred ~ Q~ or~ include rac-~ ' ' ' yll,is (2-methyl-4, 5-b~ o;~ .yl) -zirconium dichloride;
20 rac-d;ll~ l.rlailGIlJ;ylv;a (2-methylindenyl) -zirconium dichloride;
rac-.l;...~ll.yla;l~...l;yll,;s (2-methyl-4, 6-~' , u~.yl;,.~.".yl) -zirconium dichloride;
and rac-d;.l..,.h~ IV;a (2-methyl-4-phenylindenyl) -zirconium dichloride.
Exemplary ~ include illV~.O.,y~ !o~ i; ,yl titanocenes such as 24 ~ y. .1~ Alii ,.yl titanium trichloride, and the like, dimethylsilyl(tcll...r.~ .,y,,lu~ iPnyl)(t-butylamido)zirconium dimethyl (or dichloride) and the like, I,;s~y 1~ I; IYI L;ll,UIIOCC~..,.~ such as l~;a~,y~ I;r ~ ~YILh ~U~ IIII dichloride and the like.
28 In accordance with the preferred PmhorlimPnt for forming the supported catalyst, the support is dehydrated preferably at about 800C for about 18-24 hours or until a 1% or less loss on ignition value is obtained. Prior to use, the supported catalyst is dried to remove essentially all of the residual solvent which may be32 trapped in the pores of the carrier. This results in a free-flowing supported catalyst.
Once the supported catalyst is formed, it may be employed under various pol~ ,. i~l;u~ conditions. Suitable pGI ~ iOII conditions include gas phase, 36 or slurry pGlr.--~,.;~Ll;~nl. In a preferred PmhotlimPnt the supported catalyst ..... ... .. .. , . . . _ _ 2?8 WO 9~/18809 8 ~ PCT/US94/13367 prepared as described herein is contacted with alpha o~efins in a slurry pOIy~ .iL~lLioll reactor.
The invention is further illustrated by the following non limiting examples.
All ~,.,. i....,..l~ were carried out in nitrogen purged dry boxes. All solvents were purchased from ~011~11.~,. i.,~,l sources and were nitrogen purged or 8 distilled and dried over activated molecular sieves. Aluminum alkys were purchased as 20-25 wt% solutions from commercial sources. The MAO was purchased as 30 wt% in toluene from Shering Ul:)l ,UI)I d~iO~.
The polyll..,~;LdL;Ol\ procedure is as follows. In a clean, dry two liter 2 autoclave which had been flushed with propylene vapor, triethylaluminum, TEAL, (about 0.8 ml, about 1.5 M in heptane) was added and then the reactor closed andfilled with about 750 ml liquid propylene. With the reactor Iclll~ alul ~: at about 30"C the catalyst (as a 25 wt% oil slurry) was washed in via an addition tube with 16 about 250 ml propylene. The reactor was rapidly heated to about 65C. Afterthirty minutes the reactor was cooled and the excess propylene vented. The polymer was removed and dried.
Polymer analysis was carried out as described in US 5,026,798 and US
5,017,714. DSC melting points were determined on commercial DSC ill~llUIII~;
and are reported as the second melting point.
DMS (MBI) ZrC12 = d;~ll~lllyl~;l~l-J;yl bis(2-methyl-4, 5-1;~,llLU;lld~.l,~/l) zirconium dichloride.
24 P. ~ .. of DMS (MBI) 2:rCI~:
r i~tltyl meth~yl (2 ~ yllll~lllyl) n~ )n~fP (l) 5.15 g (224 mmol) of sodium were dissolved in 150 ml of absolute ethanol, 28 while heating, and 37.3 ml (217 mmol) of diethyl methylmalonate were added at room t~,...~J.,.~lLul~. A solution of 50 g (217 mmol) of 2-1,,u,,,~,,,..,.l,,~' lj ' ' ' -(96% pure) in 270 ml of ethanol was slowly added dropwise at 0C, and the mixture was heated under reflux for a further 4 to 5 hours. It was poured onto ice-32 water and extracted with ethyl acetate. The combined organic phases were dried with sodium sulfate and evaporated. After drying under an oil pump vacuum, the oily residue was stirred with hexane at 0C, whereupon 55 g (81%) ofthe compound I ~,,y , o~l Svnthesis of 2-Methyl-3-naphthvlpropjonic acid (2) A solution of 23 .7 g (422 mmol) of potassium hydroxide in 50 ml of water was added to 33.2 g (105 mmol) ofthe compound I in 70 ml of ethanol, and the 4 mixture was heated under reflux for 4 hours. After the solvent had been stripped off, the solid residue was taken up in ethyl acetate, water was added and the pHwas brought to I with l./d, U~ (llil.. acid. The aqueous phase was extracted several times with ethyl acetate. After drying over magnesium sulfate, the combined 8 organic phases were evaporated completely. The residue was $irred with hexane for crystallization. For de~a~boA~ ull~ the bei~e-colored solid was heated at 1 75C until the evolution of gas had ended. 21 g (94%) of the product 2 were obtained as a beige-colored solid.
Synthesis of 2-Methvl-6.7-benzoindan-1 -one (3) 22 ml of thionyl chloride were added to 21 g (98 mmol) of the compound 2, with exclusion of moisture, and the mixture was heated under reflux for 30 16 minutes. Excess thionyl chloride was then distilled off The residue was briefly freed from volatile compounds under an oil pump vacuum and then dissolved in 25 ml of methylene chloride, under Ar as an insert gas. The soiution was slowly âdded dropwise to a suspension of 26 g (196 mmol) of aluminum trichloride in 60 2~ ml of methylene chloride and the mixture was heated under reflux for a further 30 minutes. It was poured onto ice and extracted with methylene chloride. The combined organic phases were dried with sodium sulfate and evaporated. The dark oily residue was chromatographed on 600 g of silica gel 60. 8.6 g (45%) of the 24 compound 3 were able to be eluted (yellowish solid) with a mobile phase mixture of lI~,AI.IIJ~..IIYI acetate (9:3).
Synthesis of 2-Methvl-4.5-~,. .," 1, "~ (4) 28 2.2 g (59.5 mmol) of sodium borohydride were added in portions to a solution of 7.8 g (39.7 mmol) of the indanone, compound 3 in 400 ml of a lellallydluru~ llallol mixture (2:1 ) ât room temperature, and the mixture was stirred for 14 hours. The solution was poured onto HCL-acid ice and extracted 32 with ether. The combined organic phases were washed several times with water and dried with sodium sulfate. The orange-colored oil which remained after the solvent had been stripped oflf was dissolved in 240 ml of toluene, and the solution was heated at 8ûC with 570 mg (3 .15 mmol) of p-toluene-sulfonic acid for 15 36 minutes. It was washed several times with water at room l~ alul~, dried with WO~18809 180~98~ PCIIUS94113367 sodium sulfate and evaporated. The residue was ~,1" u..,~,lur I G"l~d on 300 g of silica gel 60. 4.7 g (65%) of the indene 4 were able to be eluted (colorless oil) with a mobile phase mixture of .~ e/ 'i.~v~ yl ether (20:1).
4 IH-N~ spectrum (360 MHz, CDCL3): 8.02 (I,d), 7.84 (I,m), 7.59 (I,d), 7.52 (I,d), 7.38-7.48 (2,m), 7.06 (I,m), 3.42 (2,s), 2.25 (3,d).
Synthesis of Pimethyibis(2-methyl-4. 5-1~ o (5) 8 10.2 ml (25.5 mmol) of a 2.5 M butyllithium solution in hexane were added to a solution of 4.6 g (25.5 mmol) of the compound 4 in 50 ml of ~ dllyd~ ~rul oll at room ~ "dlUI~, and the mixture was heated under reflux for 1 hour. The red solution was then added dropwise to a solution of 1.55 g (12 mmol) of 12 dimethyld;.,l,lulu~ ."~ in 10 ml oftetrai.~J,ufu~ at room t~"~ "alu,.i, and the rnixture was heated under reflux for 5 to 6 hours. The reaction solution was poured onto ice-water and extracted several times with ether. The combined organic phases were dried with sodium sulfate and evaporated, and the residue was 16 dried under an oil pump vacuum. It was l,lllulll~llO~,la~ d on 300g of silica gel 60.
500 mg of unreacted starting compound 4 were initially able to be eluted with a mobile phase mixture of hexane/3% ethyl acetate. The ligand system, compound 5, then followed with the same mobile phase. After the solvent had been stripped off, this ligand system was crystallized (isomers) from hexane. The yield was 1.7 g (34%, or 44% with respect to the indene, compound 4 reacted).
Synthesis of rac - D;l.,~ (2-methvl-4.5-hPn7-.-indenyl) zirçonium 24 dichlûri~to (6) 4.0 ml (10.2 mmol) of a 2.5 M butyllitllium solution in hexane were added to a solution of I .7 g (4.1 mmol) of compound 5 in 20 ml of tetrahyrofuran at room i , dLUl ~: under Ar as an inert gas, and the mixture was stirred at room 28 I~ IIUl t; for 14 hours. The residue which remained after the solvent had been stripped offwas dried using an oil pump vacuum and washed with hexane. The pale brown powder obtained was dried using an oil pump vacuum at 40 to 50C
for several hours and added to a suspension of l .0 g (4.0 mmol) of zirconium 32 lell.l~,lllvl;dc in 25 ml of methylene chloride at -78C. After the mixture had been warmed to room l~ IU~ ~, the solvent was stripped off and the residue was extracted with 20 ml of toluene in order to remove the meso form of the " . , compound 6. The residue of the toluene extract was then extracted 36 with 40 ml of methylene chloride. The solution was ~,vl~ LIal~d to a small , . .... . . . . . .. ... . . . _ . . _ .. _ .. . _ WO 9S/18809 ~ PCr/USs4/13367 volume and left to crystallize at -35C. A total of 970 mg (42%) of the L;~u~ le~ compound 6 were isolated in several fractions as the pure rdcemate.
IH NMR spectrum of the racemate (300 MHz, CDCL3): 7.96 (2,m), 7.78 (2,m), 4 7.60 (2,d), 7.48-7.56 (4,m), 7.36 (2,d), 7.27 (2,s,b-lnd-H), 2.37 (6,s,Ind-CH3), 1.36 (67s,Si-CH3). Mass spectrum: 574 M+, correct J;r,;..~t~ldli~,,., correct isotope pattern.
Gel-firee MAO was employed. A freshly separated solution of gel-free 8 MAO, decanted from a solution of gelled MAO was employed.
Eixample 1:
To a filtered solution of " DMS (MBI) ZrC12 (0.05g) in toluene 12 (75 ml) the gel-free, decanted MAO supernatant solution (30 wt % MAO, 5.3 ml) was added with stirring. After ten minutes the solution was red-orange and clear.
To this was added dehydrated silica (6.0g, Davison 948 regular, about 800C
d. hy ildLioll) and stirred about fifteen minutes. This slurry was evaporated on a 16 rotoevaporator at about 40C over about twenty five minutes at which point the slurry had reached a "mud" stage. After an additional twenty minutes drying at about 45C the solids were recovered as a light orange solid (6.59g).
~ample 2:
To a filtered solution Of " ,. ~ Cr ~ DMS (MBI) ZrC12 (. Ig) in toluene (50 ml) the clear, decanted MAO supernatant solution (30wt.% MAO, 10.6 ml) was added with stirring. After ten minutes the solution was red-orange and clear.
24 To this was added dehydrated silica (2.0g, Davison 948 regular, 800C
d~ L;O~) and stirred about fifteen minutes. This slurry was filtered and the soiids dried on a rotoevaporator at 50C. The filtrate was repeatedly added backto the solids as it dried. Final drying at 60C gdVe a red-orange solid. (2.53g).
Compardtive, Gel containing MAO catalyst pl ~ Liol~:
Example 3:
To a filtered solution of " ~ DMS (MBI) ZrC12 (0.05g) in toluene 32 (75mls), gelled MAO slurr,v resulting from uniformly agitating the bottle (30wt.%
MAO, 5.3ml) was added with stirring. After five minutes the solution was red-or4nge and slightly hazy. To this was added dehydrated silica (6.0g, Davison 948regular, 800C dehydration) and stirred about 15 minutes~ This slurry was 36 evaporated on a rotoevaporator at about 44C over about 25 minutes at which _ _ _ _ _ _ .
WO95/18809 1 %~79 8 1 PCI~/US9~/13367 point the slurry reached a "mud" stage. After about thirty five minutes additional drying at about 46C, the solids were recovered as a light orange solid. (7.2g) ~u~ aliull~ were conducted at about 65C, under the cûnditions 4 described above with the catalysts of examples I, 2 and 3. P~ . i4aliu~1 ~ with the catalysts ûf examples I and 2 resulted in free flowing, granular polymer with minimal to no residue observed on the walls of the reactor. Polymerization with the catalyst of example 3 resulted in polymer clumping and residue detected on the 8 walls of the reactor. The clumping of the polymer made it impractial to determine particle size.
The results of the poly,.,~ aliOII runs are noted in Tables I and 2 below.
Table I
Results nf FYamnl~c 1 3 Catalyst DSC
Amounta Mp Mw Example (mgs) (C) (x lo3) MWD
588 149.5 695 2.2 2100 ]49.4 704 2.4 3600 1 50.4 748 2.2 a) To give d~JplO~;Illal~ lr the same Zr amount for each run.
WO 95118809 ~ 9~ PCI/US94113367 Table 2 Particle Size Distribution EX. I EX. 2 Microns Polymer wt % Polymer wt.%
2000 2.4 0.7 1400 1.6 0.4 1000 2.4 0.6 710 3.3 1.3 500 4.7 1 7.4 354 18.1 52.5 250 32.2 22.6 1 80 26.6 3.0 125 7.4 0.6 900.7 0.4 630.2 0.1 PAN 0.2 0.1 Average 312.1 microns 376.0 microns Particle Size The examples J~"l,ol,,l,~le that the use of gel-free alumoxane solution results in (I) a supported catalyst which produces polyolefins with improved 8 ...o. ~llol~y relative to that obtained using gelled alumoxane solution and, (2) minimum to no fouling in the poly..l~i.i~l;u,. reactor. This is in contrast to use of gelled alumoxane solution which resulted in a supported catalyst producing polymer clumping on the agitator and walls of the poly"..,~ ;~I;u~ reactor and 2 wherein the polymer was not free flowing or granular in form.
The description of preferred Pmhn~' has been set forth merely to illustrate the invention and is not intended to be limiting. Upon reading the disclosure, those skilled in the art will appreciate and understand that mnriifir~tinn 16 or variations of the described embodiment will not depart from the spirit andsubstance of the invention. Although the preferred f . 1 ,o.l;" ,. . .1 ~ herein are related to 1~ . Ug~ ,UI-~ polymerization conditions, the separated, gel-free alumoxane may also be usefiully employed under l.n"l.~,g. - ~ polymerization conditions.
.. . . .. ... .. . .. .. . . ... , .. . . .. . ~ _ _ _ _ .
and are reported as the second melting point.
DMS (MBI) ZrC12 = d;~ll~lllyl~;l~l-J;yl bis(2-methyl-4, 5-1;~,llLU;lld~.l,~/l) zirconium dichloride.
24 P. ~ .. of DMS (MBI) 2:rCI~:
r i~tltyl meth~yl (2 ~ yllll~lllyl) n~ )n~fP (l) 5.15 g (224 mmol) of sodium were dissolved in 150 ml of absolute ethanol, 28 while heating, and 37.3 ml (217 mmol) of diethyl methylmalonate were added at room t~,...~J.,.~lLul~. A solution of 50 g (217 mmol) of 2-1,,u,,,~,,,..,.l,,~' lj ' ' ' -(96% pure) in 270 ml of ethanol was slowly added dropwise at 0C, and the mixture was heated under reflux for a further 4 to 5 hours. It was poured onto ice-32 water and extracted with ethyl acetate. The combined organic phases were dried with sodium sulfate and evaporated. After drying under an oil pump vacuum, the oily residue was stirred with hexane at 0C, whereupon 55 g (81%) ofthe compound I ~,,y , o~l Svnthesis of 2-Methyl-3-naphthvlpropjonic acid (2) A solution of 23 .7 g (422 mmol) of potassium hydroxide in 50 ml of water was added to 33.2 g (105 mmol) ofthe compound I in 70 ml of ethanol, and the 4 mixture was heated under reflux for 4 hours. After the solvent had been stripped off, the solid residue was taken up in ethyl acetate, water was added and the pHwas brought to I with l./d, U~ (llil.. acid. The aqueous phase was extracted several times with ethyl acetate. After drying over magnesium sulfate, the combined 8 organic phases were evaporated completely. The residue was $irred with hexane for crystallization. For de~a~boA~ ull~ the bei~e-colored solid was heated at 1 75C until the evolution of gas had ended. 21 g (94%) of the product 2 were obtained as a beige-colored solid.
Synthesis of 2-Methvl-6.7-benzoindan-1 -one (3) 22 ml of thionyl chloride were added to 21 g (98 mmol) of the compound 2, with exclusion of moisture, and the mixture was heated under reflux for 30 16 minutes. Excess thionyl chloride was then distilled off The residue was briefly freed from volatile compounds under an oil pump vacuum and then dissolved in 25 ml of methylene chloride, under Ar as an insert gas. The soiution was slowly âdded dropwise to a suspension of 26 g (196 mmol) of aluminum trichloride in 60 2~ ml of methylene chloride and the mixture was heated under reflux for a further 30 minutes. It was poured onto ice and extracted with methylene chloride. The combined organic phases were dried with sodium sulfate and evaporated. The dark oily residue was chromatographed on 600 g of silica gel 60. 8.6 g (45%) of the 24 compound 3 were able to be eluted (yellowish solid) with a mobile phase mixture of lI~,AI.IIJ~..IIYI acetate (9:3).
Synthesis of 2-Methvl-4.5-~,. .," 1, "~ (4) 28 2.2 g (59.5 mmol) of sodium borohydride were added in portions to a solution of 7.8 g (39.7 mmol) of the indanone, compound 3 in 400 ml of a lellallydluru~ llallol mixture (2:1 ) ât room temperature, and the mixture was stirred for 14 hours. The solution was poured onto HCL-acid ice and extracted 32 with ether. The combined organic phases were washed several times with water and dried with sodium sulfate. The orange-colored oil which remained after the solvent had been stripped oflf was dissolved in 240 ml of toluene, and the solution was heated at 8ûC with 570 mg (3 .15 mmol) of p-toluene-sulfonic acid for 15 36 minutes. It was washed several times with water at room l~ alul~, dried with WO~18809 180~98~ PCIIUS94113367 sodium sulfate and evaporated. The residue was ~,1" u..,~,lur I G"l~d on 300 g of silica gel 60. 4.7 g (65%) of the indene 4 were able to be eluted (colorless oil) with a mobile phase mixture of .~ e/ 'i.~v~ yl ether (20:1).
4 IH-N~ spectrum (360 MHz, CDCL3): 8.02 (I,d), 7.84 (I,m), 7.59 (I,d), 7.52 (I,d), 7.38-7.48 (2,m), 7.06 (I,m), 3.42 (2,s), 2.25 (3,d).
Synthesis of Pimethyibis(2-methyl-4. 5-1~ o (5) 8 10.2 ml (25.5 mmol) of a 2.5 M butyllithium solution in hexane were added to a solution of 4.6 g (25.5 mmol) of the compound 4 in 50 ml of ~ dllyd~ ~rul oll at room ~ "dlUI~, and the mixture was heated under reflux for 1 hour. The red solution was then added dropwise to a solution of 1.55 g (12 mmol) of 12 dimethyld;.,l,lulu~ ."~ in 10 ml oftetrai.~J,ufu~ at room t~"~ "alu,.i, and the rnixture was heated under reflux for 5 to 6 hours. The reaction solution was poured onto ice-water and extracted several times with ether. The combined organic phases were dried with sodium sulfate and evaporated, and the residue was 16 dried under an oil pump vacuum. It was l,lllulll~llO~,la~ d on 300g of silica gel 60.
500 mg of unreacted starting compound 4 were initially able to be eluted with a mobile phase mixture of hexane/3% ethyl acetate. The ligand system, compound 5, then followed with the same mobile phase. After the solvent had been stripped off, this ligand system was crystallized (isomers) from hexane. The yield was 1.7 g (34%, or 44% with respect to the indene, compound 4 reacted).
Synthesis of rac - D;l.,~ (2-methvl-4.5-hPn7-.-indenyl) zirçonium 24 dichlûri~to (6) 4.0 ml (10.2 mmol) of a 2.5 M butyllitllium solution in hexane were added to a solution of I .7 g (4.1 mmol) of compound 5 in 20 ml of tetrahyrofuran at room i , dLUl ~: under Ar as an inert gas, and the mixture was stirred at room 28 I~ IIUl t; for 14 hours. The residue which remained after the solvent had been stripped offwas dried using an oil pump vacuum and washed with hexane. The pale brown powder obtained was dried using an oil pump vacuum at 40 to 50C
for several hours and added to a suspension of l .0 g (4.0 mmol) of zirconium 32 lell.l~,lllvl;dc in 25 ml of methylene chloride at -78C. After the mixture had been warmed to room l~ IU~ ~, the solvent was stripped off and the residue was extracted with 20 ml of toluene in order to remove the meso form of the " . , compound 6. The residue of the toluene extract was then extracted 36 with 40 ml of methylene chloride. The solution was ~,vl~ LIal~d to a small , . .... . . . . . .. ... . . . _ . . _ .. _ .. . _ WO 9S/18809 ~ PCr/USs4/13367 volume and left to crystallize at -35C. A total of 970 mg (42%) of the L;~u~ le~ compound 6 were isolated in several fractions as the pure rdcemate.
IH NMR spectrum of the racemate (300 MHz, CDCL3): 7.96 (2,m), 7.78 (2,m), 4 7.60 (2,d), 7.48-7.56 (4,m), 7.36 (2,d), 7.27 (2,s,b-lnd-H), 2.37 (6,s,Ind-CH3), 1.36 (67s,Si-CH3). Mass spectrum: 574 M+, correct J;r,;..~t~ldli~,,., correct isotope pattern.
Gel-firee MAO was employed. A freshly separated solution of gel-free 8 MAO, decanted from a solution of gelled MAO was employed.
Eixample 1:
To a filtered solution of " DMS (MBI) ZrC12 (0.05g) in toluene 12 (75 ml) the gel-free, decanted MAO supernatant solution (30 wt % MAO, 5.3 ml) was added with stirring. After ten minutes the solution was red-orange and clear.
To this was added dehydrated silica (6.0g, Davison 948 regular, about 800C
d. hy ildLioll) and stirred about fifteen minutes. This slurry was evaporated on a 16 rotoevaporator at about 40C over about twenty five minutes at which point the slurry had reached a "mud" stage. After an additional twenty minutes drying at about 45C the solids were recovered as a light orange solid (6.59g).
~ample 2:
To a filtered solution Of " ,. ~ Cr ~ DMS (MBI) ZrC12 (. Ig) in toluene (50 ml) the clear, decanted MAO supernatant solution (30wt.% MAO, 10.6 ml) was added with stirring. After ten minutes the solution was red-orange and clear.
24 To this was added dehydrated silica (2.0g, Davison 948 regular, 800C
d~ L;O~) and stirred about fifteen minutes. This slurry was filtered and the soiids dried on a rotoevaporator at 50C. The filtrate was repeatedly added backto the solids as it dried. Final drying at 60C gdVe a red-orange solid. (2.53g).
Compardtive, Gel containing MAO catalyst pl ~ Liol~:
Example 3:
To a filtered solution of " ~ DMS (MBI) ZrC12 (0.05g) in toluene 32 (75mls), gelled MAO slurr,v resulting from uniformly agitating the bottle (30wt.%
MAO, 5.3ml) was added with stirring. After five minutes the solution was red-or4nge and slightly hazy. To this was added dehydrated silica (6.0g, Davison 948regular, 800C dehydration) and stirred about 15 minutes~ This slurry was 36 evaporated on a rotoevaporator at about 44C over about 25 minutes at which _ _ _ _ _ _ .
WO95/18809 1 %~79 8 1 PCI~/US9~/13367 point the slurry reached a "mud" stage. After about thirty five minutes additional drying at about 46C, the solids were recovered as a light orange solid. (7.2g) ~u~ aliull~ were conducted at about 65C, under the cûnditions 4 described above with the catalysts of examples I, 2 and 3. P~ . i4aliu~1 ~ with the catalysts ûf examples I and 2 resulted in free flowing, granular polymer with minimal to no residue observed on the walls of the reactor. Polymerization with the catalyst of example 3 resulted in polymer clumping and residue detected on the 8 walls of the reactor. The clumping of the polymer made it impractial to determine particle size.
The results of the poly,.,~ aliOII runs are noted in Tables I and 2 below.
Table I
Results nf FYamnl~c 1 3 Catalyst DSC
Amounta Mp Mw Example (mgs) (C) (x lo3) MWD
588 149.5 695 2.2 2100 ]49.4 704 2.4 3600 1 50.4 748 2.2 a) To give d~JplO~;Illal~ lr the same Zr amount for each run.
WO 95118809 ~ 9~ PCI/US94113367 Table 2 Particle Size Distribution EX. I EX. 2 Microns Polymer wt % Polymer wt.%
2000 2.4 0.7 1400 1.6 0.4 1000 2.4 0.6 710 3.3 1.3 500 4.7 1 7.4 354 18.1 52.5 250 32.2 22.6 1 80 26.6 3.0 125 7.4 0.6 900.7 0.4 630.2 0.1 PAN 0.2 0.1 Average 312.1 microns 376.0 microns Particle Size The examples J~"l,ol,,l,~le that the use of gel-free alumoxane solution results in (I) a supported catalyst which produces polyolefins with improved 8 ...o. ~llol~y relative to that obtained using gelled alumoxane solution and, (2) minimum to no fouling in the poly..l~i.i~l;u,. reactor. This is in contrast to use of gelled alumoxane solution which resulted in a supported catalyst producing polymer clumping on the agitator and walls of the poly"..,~ ;~I;u~ reactor and 2 wherein the polymer was not free flowing or granular in form.
The description of preferred Pmhn~' has been set forth merely to illustrate the invention and is not intended to be limiting. Upon reading the disclosure, those skilled in the art will appreciate and understand that mnriifir~tinn 16 or variations of the described embodiment will not depart from the spirit andsubstance of the invention. Although the preferred f . 1 ,o.l;" ,. . .1 ~ herein are related to 1~ . Ug~ ,UI-~ polymerization conditions, the separated, gel-free alumoxane may also be usefiully employed under l.n"l.~,g. - ~ polymerization conditions.
.. . . .. ... .. . .. .. . . ... , .. . . .. . ~ _ _ _ _ .
Claims (7)
1. A method for preparing a supported catalyst system comprising the steps of:
(a) removing gels from a gelled alumoxane solution; and (b) combining the resulting gel-free alumoxane solution with at least one metallocene and porous support material.
(a) removing gels from a gelled alumoxane solution; and (b) combining the resulting gel-free alumoxane solution with at least one metallocene and porous support material.
2. A method for producing a supported catalyst system comprising the steps of:
(a) removing gels from a gelled alumoxane solution; and (b) combining the resulting solution with at least one metallocene to form a reaction product; and then (c) combining the resulting reaction product with porous, dehydrated support material.
(a) removing gels from a gelled alumoxane solution; and (b) combining the resulting solution with at least one metallocene to form a reaction product; and then (c) combining the resulting reaction product with porous, dehydrated support material.
3. The method of claim 1 or 2 wherein the alumoxane is methylalumoxane and wherein the methylalumoxane is employed in a ratio of aluminum in the methylalumoxane to transition metal in the metallocene component of 12:1 to 1000:1, preferably 100:1 to 500:1.
4. The method of any of the preceding claims wherein the porous support material is silica.
5. The method of any of the preceding claims wherein the metallocene is selected from the group consisting of: rac-dimethylsilandiylbis (2-methyl-4,5-benzoindenyl)-zirconium dichloride; rac-dimethylsilandiylbis (2-methylindenyl)-zirconium dichloride; rac-dimethylsilandiylbis (2-methyl-4,6-diisopropylindenyl) -zirconium dichloride; and rac-dimethylsilandiylbis (2-methyl-4-phenylindenyl) -zirconium dichloride.
6. A method for the polymerization of olefins to polyolefins comprising the step of contacting supported catalyst obtained by the method of any one of the preceding claims with at least one olefin under suitable polymerization conditions.
7. The method of claim 6 wherein the olefin contains from 2 to about 8 carbon atoms.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US17985094A | 1994-01-11 | 1994-01-11 | |
| US179,850 | 1994-01-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2180981A1 true CA2180981A1 (en) | 1995-07-13 |
Family
ID=22658244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002180981A Abandoned CA2180981A1 (en) | 1994-01-11 | 1994-11-16 | Use of gel-free alumoxane solution |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0739346A1 (en) |
| JP (1) | JPH09507515A (en) |
| CN (1) | CN1149297A (en) |
| CA (1) | CA2180981A1 (en) |
| WO (1) | WO1995018809A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6043180A (en) * | 1994-11-17 | 2000-03-28 | The Dow Chemical Company | Supported catalyst component, supported catalyst, their preparation, and addition polymerization process |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3789666T2 (en) * | 1986-12-30 | 1994-08-04 | Mitsui Petrochemical Ind | SOLID CATALYST FOR OLEFIN POLYMERIZATION AND METHOD FOR THE PRODUCTION THEREOF. |
| US5093295A (en) * | 1989-03-23 | 1992-03-03 | Idemitsu Kosan Company Limited | Process for producing homogeneous aluminoxane solution |
| DE4004477A1 (en) * | 1990-02-14 | 1991-08-22 | Schering Ag | Solns. of oligomeric methyl-aluminoxane(s) - by partial hydrolysis of tri:methyl-aluminium with water in hydrocarbon solvent, esp. in rotor-stator reactor |
| US5235081A (en) * | 1992-03-18 | 1993-08-10 | Ethyl Corporation | Method of removing gel forming materials from methylaluminoxanes |
-
1994
- 1994-11-16 CN CN94194816A patent/CN1149297A/en active Pending
- 1994-11-16 WO PCT/US1994/013367 patent/WO1995018809A1/en not_active Application Discontinuation
- 1994-11-16 EP EP95903569A patent/EP0739346A1/en not_active Withdrawn
- 1994-11-16 CA CA002180981A patent/CA2180981A1/en not_active Abandoned
- 1994-11-16 JP JP7518473A patent/JPH09507515A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| WO1995018809A1 (en) | 1995-07-13 |
| EP0739346A1 (en) | 1996-10-30 |
| CN1149297A (en) | 1997-05-07 |
| JPH09507515A (en) | 1997-07-29 |
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