CA2263081A1 - Improved method for preparing supported metallocene catalyst systems - Google Patents
Improved method for preparing supported metallocene catalyst systems Download PDFInfo
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- CA2263081A1 CA2263081A1 CA002263081A CA2263081A CA2263081A1 CA 2263081 A1 CA2263081 A1 CA 2263081A1 CA 002263081 A CA002263081 A CA 002263081A CA 2263081 A CA2263081 A CA 2263081A CA 2263081 A1 CA2263081 A1 CA 2263081A1
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- 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
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- 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
- C08F4/62—Refractory metals or compounds thereof
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
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- 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
- C08F4/62—Refractory metals or compounds thereof
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/63916—Component covered by group C08F4/62 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
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- 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
- C08F4/62—Refractory metals or compounds thereof
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/6392—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/63922—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/63927—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
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Abstract
This invention relates generally to supported metallocene catalyst systems and to methods for their production and use. Specifically, this invention relates to a method for preparing supported metallocene catalyst systems using an aliphatic solvent. The catalyst systems prepared by these methods exhibit increased activity.
Description
CA 02263081 1999-02-0~
W O 98/13393 PCTrUS97/14533 IMPROVED METHOD FOR PREPARING SUPPORTED
METALLOCENE CATALYST SYSTEMS
FIELD OF THE ~NVENTION
This invention relates generally to supported metallocene catalyst systems and to methods for their production and use. Specifically, this invention relates to 10 methods for preparing supported metallocene catalyst systems using an aliphatic solvent.
BACKGROUND
lS A number of methods for prepalhlg supported metallocene catalyst systems have been reported. For exAmple, U. S. Patent No. 5,240,894 describes a method wherein the metallocene and activator are precolllacted and then deposited on the support material. The catalyst system is then dried to remove residual solvent and optionally prepolymerized. WO 94/28034 describes a similar 20 method wherein the metallocene is specific~lly a bridged bis indenyl compound.
U. S. Patent No. 5,373,072 describes a method involving the use of undehydrated silica gel. U. S. Patent No. 5,468,702 describes the use of an aged activator toprepare the supported metallocene catalyst system. And, U. S. Patent No.
5,516,737 describes separately supporting the activator and metallocene.
In all of these patçnt~, an aromatic hydrocarbon, typically toluene, serves as the solvent not only for the alumoxane activator but also for the metalloceneand ~ --o~Ane reaction. Typically, the metallocene and alumoxane are deposited on the support material in a toluene solution. Toluene is the solvent of choice 30 because it easily dissolves alumoxanes and/or activated metallocenes. Once the catalyst cGnlponents are deposited on the support, the catalyst system is usually -CA 02263081 1999-02-0~
W O 98/13393 PCT~US97114533 dried prior to use even though it is known that drying conditions often subst~nti~lly decrease catalyst system activity.
The present inventor has discovered that the activity of supported 5 metallocene catalyst systems is subst~nti~lly increased when an aliphatic solvent is used either in place of or in conjunction with typical solvents such as toluene.
SUMMARY
This invention relates to a method for forming a supported metallocene catalyst system comprising: (a) reacting metallocene and an alumoxane activator to form a catalyst solution; and (b) mixing the catalyst solution with support material in the presence of aliphatic solvent.
In another embodiment this invention relates to a method for forming a supported metallocene catalyst system coml~l ising: (a) reacting metallocene andan alumoxane activator to form a catalyst solution; (b) mixing aliphatic hydrocarbon solvent with support material; and (c) col,.bining the catalyst solution with the mixture.
In another embodiment this invention relates to a method for rol"ling a supported metallocene catalyst system comprising: (a) r~ ~ . ting metallocene and a first alu,,,u~ane portion to fûrm a first catalyst solution; (b) CO~ illing aliphatic solvent and support material to form a mixture; (c) con~;nillg the first catalyst 25 solution with the mixture; and then (d) adding a second alumoxane portion.
DETAILED DESCRIPTION
Catalyst System Components 5 Metallocenes As used herein "metallocene" refers generally to compounds I e~)l esenled by theformula Cp"~,Xq wherein Cp is a cyclopçnt~içnyl ring which may be substitl1tetl~ or derivative thereof which may be substitute~, M is a Group 4, 5, or 10 6 transition metal, for example tit~nil-m, zirconium, h~ m, v~n~tli--m, niobium, t~nt~ m, chromium, molybdenum and hlngcten, R is a hydrocarbyl group or hydrocarboxy group having from one to 20 carbon atoms, X is a halogen, and m=1-3, n=0-3, q=0-3, and the sum of m+n+q is equal to the oxidation state of thetransition metal.
Methods for making and using metallocenes are very well known in the art. For ~ ~!c, met~llocen~s are det~iled in United States Patent Nos.
4,530,914; 4,542,199; 4,769,910; 4,808,561; 4,871,705; 4,933,403; 4,937,299;
5,017,714; S,026,798; 5,057,475; 5,120,867; 5,278,119; 5,304,614; 5,324,800;
20 5,350,723; and 5,391,790 each fully incol~Jolaled herein by lel'elence.
P~ cd metallocenes are those l e,.)resenled by the formula:
~ (R10)4 R3~ (CR8R9)m R~CRF~8R9 )n ~(R10 ) wherein M is a metal of Group 4, 5, or 6 of the Periodic Table preferably, zirconium, h~ m and tit~ni~lm~ most preferably ~irco ~ m~;
S Rl and R2 are id~ntic~l or ~ elelll, preferably id.~ntic~l and are one of a hydrogen atom, a Cl-Clo alkyl group, prerelably a Cl-C3 alkyl group, a Cl-Clo alkoxy group, p.t;re.~bly a Cl-C3 alkoxy group, a C6-Clo aryl group, prerel~bly a C6-Cg aryl group, a C6-Clo aryloxy group, preferably a C6-Cg aryloxy group, a C2-C l o alkenyl group, prere ably a C2-C4 alkenyl group, a C7-C40 arylalkyl group, plerel~bly a C7-C1o arylalkyl group, a C7-C40 alkylaryl group, preferablya C7-C12 alkylaryl group, a Cg-C40 arylalkenyl group, prere-~ly a Cg-C12 arylalkenyl group, or a halogen atom, preferably chlorine;
~3 and R4 are hydrogen atoms;
RS and R6 are identic~l or di~~ l1, pr~rel ably id~ntic~l, are one of a halogen atom, preferably a fluorine, chlorine or bromine atom, a C l -C l o alkyl group, preferably a Cl-C4 alkyl group, which may be halogP.n~e~, a C6-Clo aryl group, which may be halo~.en~te~lJ preferably a C6-Cg aryl group, a C2-Clo alkenyl group, pler~lably a C2-C4 alkenyl group, a C7-C40 -arylalkyl group, W O 98/13393 PCTrUS97114533 preferably a C7-CIo arylalkyl group, a C7-C40 alkylaryl group, preferably a C7-C12 alkylaryl group, a Cg-C40 arylalkenyl group, plere ubly a Cg-C12 arylalkenyl group, a -NR215, -SR15, -oR15, -OSiR315 or -PR215 radical, wherein R15 is one of a halogen atom, preferably a chlorine atom, a Cl -Clo alkyl group, 5 preferably a C 1 -C3 alkyl group, or a C6-C 1 o aryl group, prerel ably a C6-Cg aryl group;
R7 is M2 ' M2 M2 ' M2 (CR213 O M2 O- , C ' ~ M2 R12 , R12 R12 -B(R1 1), -Al(Rl 1), -Ge-, -Sn-, -O-, -S-, -SO-, -S02-, -N(R1 1)-, -CO-, -10 P(Rl1)-, or-P(O)(R11)-;
wherein:
Rl 1, R12 and R13 are iclentie~l or diLre,enl and are a hydrogen atom, a hslQgçnatom, a C1-C20 alkyl group, preferably a Cl-C1o alkyl group, a Cl-C20 fluoroalkyl group, plererably a Cl-CIo fluoroalkyl group, a C6-C30 aryl group, p~er~ly a C6-C20 aryl group, a C6-C30 fluoroaryl group, prer~l~bly a C6-C20 fluoroaryl group, a Cl-C20 alkoxy group, pl~r~lably a Cl-Clo alkoxy group, a C2-C20 alkenyl group, pr~;re~ably a C2-CIo alkenyl group, a C7-C40 arylalkyl group, prere. ubly a C7-C20 arylalkyl group, a Cg-C40 arylalkenyl group, plere~..bly a Cg-C22 arylalkenyl group, a C7-C40 alkylaryl group, preferably a W O 98/13393 PCTrUS97114~33 C7-C20 allylaryl group or Rl 1 and R12, or Rl 1 and R13, together with the atoms binding them, can form ring systems;
M2 is silicon, ge~ ni~lm or tin, prerelably silicon or ge~ m, most 5 preferably silicon;
R8 and R9 are identis~l or dill~renl and have the m~ning~ stated for Rl l;
m and n are idçntic~l or di~l enl and are zero, 1 or 2, preferably zero or 1, 10 m plus n being zero, 1 or 2, p-efe,ably zero or 1; and the radicals R10 are id~ntic~l or di~erelll and have the me~n;ng~ stated for R11, Rl2 and R13. Two adjac~nt R10 radicals can bejoined together to form a ring system, p~Ç~;Iably a ring system cont~ining from 4-6 carbon atoms.
Alkyl refers to straight or branched chain substitl-çnt~ Halogen (halo~Pnated) refers to fluorine, chlorine, bromine or iodine atoms, preferably fluorine or chlorine.
Particularly prere - ed metallocenes are compounds of the structures (A) and (B):
~ ,,... , ~ .........
W O 98113393 PCT~US97/14533 R5 ~ R1 ~ ~ (R10)4 ~R2 (A) R12 ~ ~ ~R2 (B) R11 R12C~R6 \~y6 ~ (R10)4 ~ (R1 o)4 wherein:
M1 is Zr or Hf, Rl and R2 are methyl or chlorine, and RS, R6 R8, R9,R10, R11 and R12 have the above-mentioned me~n;~
These chiral metallocenes may be used as a rac~m~te for the prepa, ~lion of highly isotactic polypropylene copolymers. It is also possible to use the pure R or S form. An optically active polymer can be prel)aled with these pure 10 stereoisomeric forms. ~1 er~l~bly the meso form of the metallocene is removed to ensure the center (i.e., the metal atom) provides steleole~,llar pol~"~ lion.
Separation of the stereoisomers can be accompli~hed by known 1iterature teçhn;~nes. For special products it is also possible to use rac/meso mixtures.
Generally, these metallocenes are pl~,pdlC~ by a multi-step process involving repeated deprotonationslmet~ tions ofthe aromatic ligands and introduction of the bridge and the central atom by their halogen derivatives. The following reaction scheme illustrates this generic approach:
H2RC + ButyLi ~-------> HRCLi X-(CR8R9)m-R7-(CR8R9)n-X
__________________ ~
H2Rd + ButyLi __-----> ~dLi HRC-(CR8R9)m-R7-(CR8R9)n-RdH 2 Butyl ~i _ _ _ _ _ _ _~
LiRC-(CR8R9)m-R7-(CR8R9)n-RdLi M 1 C4 S _ _ _ _ _ _ _~
(R8R9C)m--~c (R8R9C)m ,RC
R7 M1~ R~ Li 1 7 M1~ R1 ' ~Cl I I ~Cl R8R9C)n Rd (R8R9C)n Rd (R8R9C)m RC
R2Li~ 17 M1~R2 j ~ R2 (R8R9C)n Rd X = Cl,Br,lorO-tosyl; H2RC ~R3 Additional methotlc for prep&~ g metallocenes are fi~lly described in the Journal of Or~anometallic Chem., volume 288, (1985), pages 63-67, and in EP-A-10 320762, both of which are herein fully incorporated by reference.
Illustrative but non-~i~nitin~ examples of prert;l.ed metallocenes include:
Dimethylsilandiylbis(2-methyl-4-phenyl- 1 -indenyl)ZrC12 Dimethylsilandiylbis(2-methyl-4,5-benzoindenyl)ZrC12;
Dimethylsilandiylbis(2-methyl-4,6-diisopropylindenyl)ZrC12;
Dimethylsilandiylbis(2-ethyl-4-phenyl-1-indenyl)ZrC12;
Dimethylsilandiylbis (2-ethyl-4-naphthyl-1-indenyl)ZrCl2, Phenyl(methyl)silandiylbis(2-methyl-4-phenyl- 1 -indenyl)ZrC12, CA 02263081 1999-02-0~
W O 98/13393 PCT~US97114S33 Dimethylsilandiylbis(2-methyl-4-( 1 -naphthyl)- I -indenyl)zrcl2~
Dimethylsilandiylbis(2-methyl-4-(2-naphthyl)-1-indenyl)ZrCl2, Dimethylsilandiylbis(2-methyl-indenyl)ZrC12, ~ Dimethylsilandiylbis(2-methyl4, S-diisopropyl- I -indenyl)zrcl2 5 Dimethylsilandiylbis(2,4,6-trimethyl- 1 -indenyl)zrcl2~
Phenyl(methyl)silandiylbis(2-methyl-4,6-diisopropyl- 1 -indenyl)ZrC12, I ,2-F.th~n-liylbis(2-methyl-4,6-diisopropyl-1 -indenyl)zrcl2~
I ,2-Butandiylbis(2-methyl-4,6-diisopropyl- 1 -indenyl)ZrC12, Dimethylsilandiylbis(2-methyl-4-ethyl- 1 -indenyl)Zrcl2~
Dimethylsilandiylbis(2-methyl-4-isopropyl- 1 -indenyl)ZrC12, Dimethylsilandiylbis(2-methyl-4-t-butyl- 1 -indenyl)ZrC12, Phenyl(methyl)silandiylbis(2-methyl-4-isopropyl- 1 -indenyl)zrcl2 Dimethylsilandiylbis(2-ethyl-4-methyl-1-indenyl)ZrC12, Dimethylsilandiylbis(2,4-dimethyl- 1-indenyl)ZrC12, l S Dimethylsilandiylbis(2-methyl-4-ethyl- 1 -indenyl)Zrcl2~
Dimethylsilandiylbis(2-methyl-a-acenaphth- 1 -indenyl)ZrC12, Phenyl(methyl)silandiylbis(2-methyl-4,5-benzo- 1 -indenyl)ZrC12, Phenyl(methyl)silandiylbis(2-methyl-4,5-(methylbenzo)- 1 -indenyl)ZrC12, Phenyl(methyl)silandiylbis(2-methyl-4,5-(tetramelLylbel zo)-1-indenyl)ZrC12, 20 Phenyl(methyl)silandiylbis(2-methyl-a-acenaphth- 1 -indenyl)zrcl2 I ,2-F.thqn-liylbis(2-methyl-4,5-benzo- 1 -indenyl)ZrC12, 1,2-R~Itvndiylbis(2-methyl-4,5-benzo-l -indenyl)zrcl2~
Dimeth;ls;lalldiylbis(2-methyl-4,5-benzo-1-indenyl)ZrC12, 1 ,2-F.th~n~liylbis(2,4,7-1~ clhyl- 1 -indenyl)ZrC12, 25 Dimethylsilandiylbis(2-methyl- 1 -indenyl)zrcl2 1,2-F.th~-.1iylbis(2-methyl-1 -indenyl)ZrC12, Phenyl(methyl)silandiylbis(2-methyl-l-indenyl)zrcl2 Diphenylsilandiylbis(2-methyl- 1 -indenyl)ZrC12, 1,2-R~Itqn-liylbis(2-methyl- 1-indenyl)ZrC12, Dimethylsilandiylbis(2-ethyl- l-indenyl)zrcl2~
Dimethylsilandiylbis(2-methyl-5-isobutyl-1-indenyl)ZrC12, Phenyl(methyl)silandiylbis(2-methyl-S-isobutyl- 1 -indenyl)ZrC12, Dimethylsilandiylbis(2-methyl-5-t-butyl- 1 -indenyl~ZrC12, S Dimethylsilandiylbis(2,5,6-trimethyl-1-indenyl)ZrC12, and the like.
These plt;re-led metallocene catalyst col.lpollents are described in detail in U.S. Patent Nos. 5,145,819; 5,243,001; 5,239,022; 5,329,033; 5,296,434;
5,276,208; and 5,374,752; and EP 549 900 and 576 970 all of which are herein 10 fully incorporated by lerelellce.
Ac1ivators Metallocenes are generally used in colllbination with some form of I S activator in order to create an active catalyst system. The term "activator" is defined herein to be any compound or component, or co-nbillalion of compounds or components, capable of çnh~ncing the ability of one or more metallocenes to polymerize olefins to polyolefins. For this invention, alklyalumoxanes are preferably used as activators, most plerelably methylalumoxane (MAO).
20 Generally, alkylalumoxanes contain S to 40 of the repeating units:
--R ( ~I~)x--AIR2 for linear species and ~( ~1--Otx- for cyclic species where R is a Cl-Cg alkyl inc~ ing mixed alkyls. Particularly plere.led are the compounds in which R is methyl. Alumoxane solutions, particularly methylalumoxane solutions, may be obtained from commercial vendors as 5 solutions having various conce~ tions. There are a variety of methods for prep&.hlg alumoxane, non-limiting examples of which are described in U.S. PatentNo. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031 and EP-A-0 561 476, EP-Bl-0 279 5~6, EP-A-0 594-218 and WO 94/101 ~0, each fillly incorporated herein by reference. (as used herein unless otherwise stated "solution" refers to any mixture incllu~ling suspensions.) Suppor~ Materials The support materials used in the methods of this invention are preferably porous particulate materials, such as for c~ llpl~, talc, il~orgallic oxides, inorganic chlorides and resinous materia}s such as polyolefin or polymeric compounds.
The most p~rell~d support materials are porous inorganic oxide materials, 20 which include those from the Periodic Table of F.lem~nt~ of Groups 2, 3, 4, 5, 13 or 14 metal oxides. Silica, plllmin~ silica-~l~-min~ and mixtures thereof are particularly p, eLI l ed. Other inorg,dluc oxides that may be employed either alone or in co~ alion with the silica, ~IIImin~ or silica-~ min~ are ma$rle~ ;~ titania, ~,conia, and the like.
~ leîel~bly the support material is porous silica which has a surface area in the range of from 10 to 700 m2/g, a total pore volume in the range of from 0.1 to 4.0 cc/g and an average particle rli~meter in the range of from 10 to 500 llm.
More p.~fel~bly, the surface area is in the range of ~om 50 to 500 m2/g, the 30 pore volume is in the range of from 0.5 to 3.5 cc/g and the average particle tli~rnetçr is in the range of from 20 to 200 ~m. Most preferably the surface area W 0 98/13393 PCT~US97/14533 is in the range of ~om 100 to 400 m2/g, the pore volume is in the range of from 0.8 to 3.0 cc/g and the average particle fli~met~r is in the range of from 30 to100 ~m. The average pore di~meter oftypical porous support materials is in the range offrom 10 to 1000A. Preferably, a support material is used that has an S average pore di~nleter of from 50 to 500R, and most preferably ~om 75 to 3soA. It may be particularly desirable to dehydrate the silica at a te..lpe.~ re of from 1 00~C to 800~C anywhere from 3 to 24 hours.
Met~todfor Preparing the Catalyst Sysfem The methods of this invention are di~tin~ hed by the use of an aliphatic hydrocarbon solvent during the pl epa.alion of the catalyst system. Surprisingly, the reslllting catalyst systems have a markedly increased activity co.l.pared toconventionally prepared metallocene catalyst systems.
Preferably, the ratio of the total volume of aliphatic hydrocarbon to aromatic hydrocarbon used to prepal e the catalyst system is at least 1:1, more plcrel..bly in the range offrom 1:1 to 10:1 or more, even more l~lerel~bly from 2:1 to 8:1, even more preferably from 3:1 to 5:1.
Any aliphatic hydrocarbon or mixture of aliphatic hydrocarbons can be used in the methods ofthis invention. F'~,re.~bly the aliphatic hydrocarbon is aC3-Clo alkane. More p.t;re-~ly the aliphatic hydrocarbon is s~lected from the group concic~ing of pc~llanc, hexane, he~ e, isopclllane, cyclohexane, octane, 25 i~obut~ne, butane, and propane. Most p- ~rel ~bly the aliphatic hydrocarbon is selected ~om the group con~ of: isGpe.llanc, pentane, hexane, hcplane and isobutane.
Alumoxane is typically dissolved in toluene as a 10% to 30 % solution.
30 Preferably a 30% solution of alumoxane, pl crcl ~bly methyl~ll .mox~ne, is used to _, ~ .
minimi7e the volume ofto}uene. At higher alumoxane concentrations, gels tend to form.
The metallocene and ~ mo~ne may be independently contacted with the 5 support with either the metallocene or the alumoxane contacted first or the three components may be mixed together at one time. Likewise the aliphatic hydrocarbon solvent may be indepentlently contacted with the three components or with any combination of components. Thus the precipitation can occur either in the presence of the support, prior to contact with the support, or a~er one or lO more of the components are supported. Preferably, however, the metallocene and alumoxane are precGnlacted in an aromatic hydrocarbon solvent and their reactionproduct is mixed with the support. This is particularly prt;rw I ed when the metallocene alone is either insoluble or spa.ingly soluble in both aliphatic andaromatic hydrocalbons. It is also prer~,able to contact the metallocene and 15 alumoxane in solution, i.e., an aromatic hydrocarbon solution such as toluene.
The aliphatic hydrocarbon is preferably mixed with the support material and the metallocene/~ ..oxA~-e reaction product solution combined with the support at which point prtci,oilalion occurs.
In an alternative embodiment the total amount of alumoxane used to activate the metallocene is split into two portions which are appl o~ alely equal.
The first portion is reacted with the metallocene in solution to form a reactionproduct which is then mixed with a slurly of support material in aliphatic hydrocarbon. ~he second alumoxane portion is then added.
Regardless of which of the above methods is used, once all of the catalyst colllpol1cllls are coll~ ed, the ln".l~lre is easier to mix if a slurry is forrned. To f~çilit~te drying, however, it is preferable to use as little overall liquid as possible.
Thus, when using porous support material, it is pre~lled that the total volume of liquid (both aromatic and aliphatic hydrocarbon) applied to the support is less than 5 times the total pore volume of the porous support, more pl e~, dbly less than 4 times the total pore volume ofthe porous support and even more p-~rtlabl~ less than 3 times the total pore volume of the porous support. Procedures for measuring the total pore volume of porous support are well known in the art. Thep-ert;,l ~d method is described in Volume 1, Experimen~al Methods in Catalyst Rese.l, ~h, ~ dPmic Press, 1968, pages 67-96.
In pl ere" ed embodinlel-ls, the metallocene and activator are pr~colllacted and allowed to react in solution for a time period ranging from 1 minute to 16 hours, more prefe,ably at least 10 minl~tes, and most preferably 10 min-ltes to hour. Likewise, it is prere,dble to mix the metallocene/alumoxane reaction 10 product with a hexane slurry of support material and allow the mixture to sit for at least 10 min-ltes, p,e~el~ly 10 minlltes to one hour. If the alumoxane is split into portions, then again, it is preferable to allow the second portion to react with the metallocene/alumoxanelsupport material mixture for at least 10 minutçs, pre~rdbly 10 mimltes to 1 hour.
Once all of the co"ll)onents inrl~lding the aliphatic hydrocarbon are con~ ed, the catalyst system is p-c;rt;l ~bly dried although the catalyst system can be used directly in polyrnerization. If the catalyst system is dried or allowed to dry, preferably little or no heat is used. The exact drying conditions will depend 20 on the specific embodiment, the size of the catalyst batch, and the amount of liquid but in every in~t~nce it is plerel~ble to use little or no heat for the least amount of time possible. A vacuum or purge of inert gas such as nitrogen may be used but, again, it is preferable to use these sparingly to avoid co~ tion and reduction in catalyst activity.
The supported catalyst system may be used directly in polymerization or the catalyst system may be prepolyrnerized using methods well known in the art.
For details regarding prepolyl~ ion, see United States Patent Nos. 4,923,833 and 4,921,825, EP 0 279 863 and EP 0 354 893 each of which is fully 30 incorporated herein by l~r~le.lce.
. .
In an alternative embodiment, the catalyst system is prepaled using an olefin promoter as a metallocene reactant. This method has also has been found by the present inventor to lead to increased activity as described in copending U.S.
Patent Application No. ("Improved Metallocene Catalyst Systems" filed 5 on the same day as this application by the same inventor - fully i.,col~lo,~led herein by IGrG Gllce).
Polymerizal'ion and Ca~alyst System Performance The catalyst system prepaled by the methods ofthis invention may be used in the polymerization of any monomer and optionally comonomers in any process in~lu~ing gas, slurry or solution phase or high pressure autoclave processes. (As used herein, unless difrer~ te~l, "polymerization" in~ dçs copoly,..Gli,.~Lion and "mono",e." ineludes co-"ol1o,--er.) Preferably, a gas or slurry phase process is15 used, most p. c;re, ~Iy a bulk liquid propylene polylllcl i~dlion process is used.
In the prere" ed embodiment, this invention is directed toward the bulk liquid poly,..e. i~lion and copol~...el i~lion of propylene or ethylene, particularly propylene, in a slurry or gas phase poly..,e.i~dlion process, particularly a slurry 20 polymerization process. Another embodiment involves copolymerization reactions of propylene or ethylene, particularly propylene, with one or more ofthe alpha-olefin ,..onG."ers having from 4 to 20 carbon atoms, p,Gre,..bly 4-12 carbon atoms, for ex~ml le alpha-olefin comono,..e.~ of ethylene, butene-1, pentene-1, 4-methylpentene-1, hexene-l, octene-1, decene-1, and cyclic olefins such as styrene, cyclopentene or noll oll.~,ne. Other suitable monomers include polar vinyl, diolefins such as dienes, for e~l,?le, 1,3-b~lt~içne, 1,4-hexadiene, norborn~diçne or vi~,ylno,l,o~"~,ne, acetylene and aldehyde monomers.
In another embodiment ethylene or propylene is polymerized with at least - 30 two different comono",c~ to form a terpolymer and the like, the plGr~lled comonomers are a cG..lbhlation of alpha-olefin mono,.,G, ~ having 3 to 10 carbon CA 0226308l l999-02-0~
atoms, more prt;re- ~bly 3 to 8 carbon atoms, and/or dienes having 4 to 10 carbon atoms.
Typically in a gas phase polymerization process a continllous cycle is 5 employed where in one part of the cycle of a reactor, a cycling gas stream, otherwise known as a recycle stream or fluidizing medium, is heated in the reactor by the heat of polymerization. The recycle stream usually contains one or more monomers continuously cycled through a fl-lidi7ed bed in the plesence of a catalyst under reactive conditions. This heat is removed in another part of the 10 cycle by a cooling system external to the reactor The recycle stream is withdrawn from the fl.liAi7ed bed and recycled back into the reactor. Siml.lt~neously, polymer product is withdrawn from the reactor and new or fresh monomer is added to replace the polymerized monomer. (See for example U.S. Patent Nos. 4,543,399;
W O 98/13393 PCTrUS97/14533 IMPROVED METHOD FOR PREPARING SUPPORTED
METALLOCENE CATALYST SYSTEMS
FIELD OF THE ~NVENTION
This invention relates generally to supported metallocene catalyst systems and to methods for their production and use. Specifically, this invention relates to 10 methods for preparing supported metallocene catalyst systems using an aliphatic solvent.
BACKGROUND
lS A number of methods for prepalhlg supported metallocene catalyst systems have been reported. For exAmple, U. S. Patent No. 5,240,894 describes a method wherein the metallocene and activator are precolllacted and then deposited on the support material. The catalyst system is then dried to remove residual solvent and optionally prepolymerized. WO 94/28034 describes a similar 20 method wherein the metallocene is specific~lly a bridged bis indenyl compound.
U. S. Patent No. 5,373,072 describes a method involving the use of undehydrated silica gel. U. S. Patent No. 5,468,702 describes the use of an aged activator toprepare the supported metallocene catalyst system. And, U. S. Patent No.
5,516,737 describes separately supporting the activator and metallocene.
In all of these patçnt~, an aromatic hydrocarbon, typically toluene, serves as the solvent not only for the alumoxane activator but also for the metalloceneand ~ --o~Ane reaction. Typically, the metallocene and alumoxane are deposited on the support material in a toluene solution. Toluene is the solvent of choice 30 because it easily dissolves alumoxanes and/or activated metallocenes. Once the catalyst cGnlponents are deposited on the support, the catalyst system is usually -CA 02263081 1999-02-0~
W O 98/13393 PCT~US97114533 dried prior to use even though it is known that drying conditions often subst~nti~lly decrease catalyst system activity.
The present inventor has discovered that the activity of supported 5 metallocene catalyst systems is subst~nti~lly increased when an aliphatic solvent is used either in place of or in conjunction with typical solvents such as toluene.
SUMMARY
This invention relates to a method for forming a supported metallocene catalyst system comprising: (a) reacting metallocene and an alumoxane activator to form a catalyst solution; and (b) mixing the catalyst solution with support material in the presence of aliphatic solvent.
In another embodiment this invention relates to a method for forming a supported metallocene catalyst system coml~l ising: (a) reacting metallocene andan alumoxane activator to form a catalyst solution; (b) mixing aliphatic hydrocarbon solvent with support material; and (c) col,.bining the catalyst solution with the mixture.
In another embodiment this invention relates to a method for rol"ling a supported metallocene catalyst system comprising: (a) r~ ~ . ting metallocene and a first alu,,,u~ane portion to fûrm a first catalyst solution; (b) CO~ illing aliphatic solvent and support material to form a mixture; (c) con~;nillg the first catalyst 25 solution with the mixture; and then (d) adding a second alumoxane portion.
DETAILED DESCRIPTION
Catalyst System Components 5 Metallocenes As used herein "metallocene" refers generally to compounds I e~)l esenled by theformula Cp"~,Xq wherein Cp is a cyclopçnt~içnyl ring which may be substitl1tetl~ or derivative thereof which may be substitute~, M is a Group 4, 5, or 10 6 transition metal, for example tit~nil-m, zirconium, h~ m, v~n~tli--m, niobium, t~nt~ m, chromium, molybdenum and hlngcten, R is a hydrocarbyl group or hydrocarboxy group having from one to 20 carbon atoms, X is a halogen, and m=1-3, n=0-3, q=0-3, and the sum of m+n+q is equal to the oxidation state of thetransition metal.
Methods for making and using metallocenes are very well known in the art. For ~ ~!c, met~llocen~s are det~iled in United States Patent Nos.
4,530,914; 4,542,199; 4,769,910; 4,808,561; 4,871,705; 4,933,403; 4,937,299;
5,017,714; S,026,798; 5,057,475; 5,120,867; 5,278,119; 5,304,614; 5,324,800;
20 5,350,723; and 5,391,790 each fully incol~Jolaled herein by lel'elence.
P~ cd metallocenes are those l e,.)resenled by the formula:
~ (R10)4 R3~ (CR8R9)m R~CRF~8R9 )n ~(R10 ) wherein M is a metal of Group 4, 5, or 6 of the Periodic Table preferably, zirconium, h~ m and tit~ni~lm~ most preferably ~irco ~ m~;
S Rl and R2 are id~ntic~l or ~ elelll, preferably id.~ntic~l and are one of a hydrogen atom, a Cl-Clo alkyl group, prerelably a Cl-C3 alkyl group, a Cl-Clo alkoxy group, p.t;re.~bly a Cl-C3 alkoxy group, a C6-Clo aryl group, prerel~bly a C6-Cg aryl group, a C6-Clo aryloxy group, preferably a C6-Cg aryloxy group, a C2-C l o alkenyl group, prere ably a C2-C4 alkenyl group, a C7-C40 arylalkyl group, plerel~bly a C7-C1o arylalkyl group, a C7-C40 alkylaryl group, preferablya C7-C12 alkylaryl group, a Cg-C40 arylalkenyl group, prere-~ly a Cg-C12 arylalkenyl group, or a halogen atom, preferably chlorine;
~3 and R4 are hydrogen atoms;
RS and R6 are identic~l or di~~ l1, pr~rel ably id~ntic~l, are one of a halogen atom, preferably a fluorine, chlorine or bromine atom, a C l -C l o alkyl group, preferably a Cl-C4 alkyl group, which may be halogP.n~e~, a C6-Clo aryl group, which may be halo~.en~te~lJ preferably a C6-Cg aryl group, a C2-Clo alkenyl group, pler~lably a C2-C4 alkenyl group, a C7-C40 -arylalkyl group, W O 98/13393 PCTrUS97114533 preferably a C7-CIo arylalkyl group, a C7-C40 alkylaryl group, preferably a C7-C12 alkylaryl group, a Cg-C40 arylalkenyl group, plere ubly a Cg-C12 arylalkenyl group, a -NR215, -SR15, -oR15, -OSiR315 or -PR215 radical, wherein R15 is one of a halogen atom, preferably a chlorine atom, a Cl -Clo alkyl group, 5 preferably a C 1 -C3 alkyl group, or a C6-C 1 o aryl group, prerel ably a C6-Cg aryl group;
R7 is M2 ' M2 M2 ' M2 (CR213 O M2 O- , C ' ~ M2 R12 , R12 R12 -B(R1 1), -Al(Rl 1), -Ge-, -Sn-, -O-, -S-, -SO-, -S02-, -N(R1 1)-, -CO-, -10 P(Rl1)-, or-P(O)(R11)-;
wherein:
Rl 1, R12 and R13 are iclentie~l or diLre,enl and are a hydrogen atom, a hslQgçnatom, a C1-C20 alkyl group, preferably a Cl-C1o alkyl group, a Cl-C20 fluoroalkyl group, plererably a Cl-CIo fluoroalkyl group, a C6-C30 aryl group, p~er~ly a C6-C20 aryl group, a C6-C30 fluoroaryl group, prer~l~bly a C6-C20 fluoroaryl group, a Cl-C20 alkoxy group, pl~r~lably a Cl-Clo alkoxy group, a C2-C20 alkenyl group, pr~;re~ably a C2-CIo alkenyl group, a C7-C40 arylalkyl group, prere. ubly a C7-C20 arylalkyl group, a Cg-C40 arylalkenyl group, plere~..bly a Cg-C22 arylalkenyl group, a C7-C40 alkylaryl group, preferably a W O 98/13393 PCTrUS97114~33 C7-C20 allylaryl group or Rl 1 and R12, or Rl 1 and R13, together with the atoms binding them, can form ring systems;
M2 is silicon, ge~ ni~lm or tin, prerelably silicon or ge~ m, most 5 preferably silicon;
R8 and R9 are identis~l or dill~renl and have the m~ning~ stated for Rl l;
m and n are idçntic~l or di~l enl and are zero, 1 or 2, preferably zero or 1, 10 m plus n being zero, 1 or 2, p-efe,ably zero or 1; and the radicals R10 are id~ntic~l or di~erelll and have the me~n;ng~ stated for R11, Rl2 and R13. Two adjac~nt R10 radicals can bejoined together to form a ring system, p~Ç~;Iably a ring system cont~ining from 4-6 carbon atoms.
Alkyl refers to straight or branched chain substitl-çnt~ Halogen (halo~Pnated) refers to fluorine, chlorine, bromine or iodine atoms, preferably fluorine or chlorine.
Particularly prere - ed metallocenes are compounds of the structures (A) and (B):
~ ,,... , ~ .........
W O 98113393 PCT~US97/14533 R5 ~ R1 ~ ~ (R10)4 ~R2 (A) R12 ~ ~ ~R2 (B) R11 R12C~R6 \~y6 ~ (R10)4 ~ (R1 o)4 wherein:
M1 is Zr or Hf, Rl and R2 are methyl or chlorine, and RS, R6 R8, R9,R10, R11 and R12 have the above-mentioned me~n;~
These chiral metallocenes may be used as a rac~m~te for the prepa, ~lion of highly isotactic polypropylene copolymers. It is also possible to use the pure R or S form. An optically active polymer can be prel)aled with these pure 10 stereoisomeric forms. ~1 er~l~bly the meso form of the metallocene is removed to ensure the center (i.e., the metal atom) provides steleole~,llar pol~"~ lion.
Separation of the stereoisomers can be accompli~hed by known 1iterature teçhn;~nes. For special products it is also possible to use rac/meso mixtures.
Generally, these metallocenes are pl~,pdlC~ by a multi-step process involving repeated deprotonationslmet~ tions ofthe aromatic ligands and introduction of the bridge and the central atom by their halogen derivatives. The following reaction scheme illustrates this generic approach:
H2RC + ButyLi ~-------> HRCLi X-(CR8R9)m-R7-(CR8R9)n-X
__________________ ~
H2Rd + ButyLi __-----> ~dLi HRC-(CR8R9)m-R7-(CR8R9)n-RdH 2 Butyl ~i _ _ _ _ _ _ _~
LiRC-(CR8R9)m-R7-(CR8R9)n-RdLi M 1 C4 S _ _ _ _ _ _ _~
(R8R9C)m--~c (R8R9C)m ,RC
R7 M1~ R~ Li 1 7 M1~ R1 ' ~Cl I I ~Cl R8R9C)n Rd (R8R9C)n Rd (R8R9C)m RC
R2Li~ 17 M1~R2 j ~ R2 (R8R9C)n Rd X = Cl,Br,lorO-tosyl; H2RC ~R3 Additional methotlc for prep&~ g metallocenes are fi~lly described in the Journal of Or~anometallic Chem., volume 288, (1985), pages 63-67, and in EP-A-10 320762, both of which are herein fully incorporated by reference.
Illustrative but non-~i~nitin~ examples of prert;l.ed metallocenes include:
Dimethylsilandiylbis(2-methyl-4-phenyl- 1 -indenyl)ZrC12 Dimethylsilandiylbis(2-methyl-4,5-benzoindenyl)ZrC12;
Dimethylsilandiylbis(2-methyl-4,6-diisopropylindenyl)ZrC12;
Dimethylsilandiylbis(2-ethyl-4-phenyl-1-indenyl)ZrC12;
Dimethylsilandiylbis (2-ethyl-4-naphthyl-1-indenyl)ZrCl2, Phenyl(methyl)silandiylbis(2-methyl-4-phenyl- 1 -indenyl)ZrC12, CA 02263081 1999-02-0~
W O 98/13393 PCT~US97114S33 Dimethylsilandiylbis(2-methyl-4-( 1 -naphthyl)- I -indenyl)zrcl2~
Dimethylsilandiylbis(2-methyl-4-(2-naphthyl)-1-indenyl)ZrCl2, Dimethylsilandiylbis(2-methyl-indenyl)ZrC12, ~ Dimethylsilandiylbis(2-methyl4, S-diisopropyl- I -indenyl)zrcl2 5 Dimethylsilandiylbis(2,4,6-trimethyl- 1 -indenyl)zrcl2~
Phenyl(methyl)silandiylbis(2-methyl-4,6-diisopropyl- 1 -indenyl)ZrC12, I ,2-F.th~n-liylbis(2-methyl-4,6-diisopropyl-1 -indenyl)zrcl2~
I ,2-Butandiylbis(2-methyl-4,6-diisopropyl- 1 -indenyl)ZrC12, Dimethylsilandiylbis(2-methyl-4-ethyl- 1 -indenyl)Zrcl2~
Dimethylsilandiylbis(2-methyl-4-isopropyl- 1 -indenyl)ZrC12, Dimethylsilandiylbis(2-methyl-4-t-butyl- 1 -indenyl)ZrC12, Phenyl(methyl)silandiylbis(2-methyl-4-isopropyl- 1 -indenyl)zrcl2 Dimethylsilandiylbis(2-ethyl-4-methyl-1-indenyl)ZrC12, Dimethylsilandiylbis(2,4-dimethyl- 1-indenyl)ZrC12, l S Dimethylsilandiylbis(2-methyl-4-ethyl- 1 -indenyl)Zrcl2~
Dimethylsilandiylbis(2-methyl-a-acenaphth- 1 -indenyl)ZrC12, Phenyl(methyl)silandiylbis(2-methyl-4,5-benzo- 1 -indenyl)ZrC12, Phenyl(methyl)silandiylbis(2-methyl-4,5-(methylbenzo)- 1 -indenyl)ZrC12, Phenyl(methyl)silandiylbis(2-methyl-4,5-(tetramelLylbel zo)-1-indenyl)ZrC12, 20 Phenyl(methyl)silandiylbis(2-methyl-a-acenaphth- 1 -indenyl)zrcl2 I ,2-F.thqn-liylbis(2-methyl-4,5-benzo- 1 -indenyl)ZrC12, 1,2-R~Itvndiylbis(2-methyl-4,5-benzo-l -indenyl)zrcl2~
Dimeth;ls;lalldiylbis(2-methyl-4,5-benzo-1-indenyl)ZrC12, 1 ,2-F.th~n~liylbis(2,4,7-1~ clhyl- 1 -indenyl)ZrC12, 25 Dimethylsilandiylbis(2-methyl- 1 -indenyl)zrcl2 1,2-F.th~-.1iylbis(2-methyl-1 -indenyl)ZrC12, Phenyl(methyl)silandiylbis(2-methyl-l-indenyl)zrcl2 Diphenylsilandiylbis(2-methyl- 1 -indenyl)ZrC12, 1,2-R~Itqn-liylbis(2-methyl- 1-indenyl)ZrC12, Dimethylsilandiylbis(2-ethyl- l-indenyl)zrcl2~
Dimethylsilandiylbis(2-methyl-5-isobutyl-1-indenyl)ZrC12, Phenyl(methyl)silandiylbis(2-methyl-S-isobutyl- 1 -indenyl)ZrC12, Dimethylsilandiylbis(2-methyl-5-t-butyl- 1 -indenyl~ZrC12, S Dimethylsilandiylbis(2,5,6-trimethyl-1-indenyl)ZrC12, and the like.
These plt;re-led metallocene catalyst col.lpollents are described in detail in U.S. Patent Nos. 5,145,819; 5,243,001; 5,239,022; 5,329,033; 5,296,434;
5,276,208; and 5,374,752; and EP 549 900 and 576 970 all of which are herein 10 fully incorporated by lerelellce.
Ac1ivators Metallocenes are generally used in colllbination with some form of I S activator in order to create an active catalyst system. The term "activator" is defined herein to be any compound or component, or co-nbillalion of compounds or components, capable of çnh~ncing the ability of one or more metallocenes to polymerize olefins to polyolefins. For this invention, alklyalumoxanes are preferably used as activators, most plerelably methylalumoxane (MAO).
20 Generally, alkylalumoxanes contain S to 40 of the repeating units:
--R ( ~I~)x--AIR2 for linear species and ~( ~1--Otx- for cyclic species where R is a Cl-Cg alkyl inc~ ing mixed alkyls. Particularly plere.led are the compounds in which R is methyl. Alumoxane solutions, particularly methylalumoxane solutions, may be obtained from commercial vendors as 5 solutions having various conce~ tions. There are a variety of methods for prep&.hlg alumoxane, non-limiting examples of which are described in U.S. PatentNo. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031 and EP-A-0 561 476, EP-Bl-0 279 5~6, EP-A-0 594-218 and WO 94/101 ~0, each fillly incorporated herein by reference. (as used herein unless otherwise stated "solution" refers to any mixture incllu~ling suspensions.) Suppor~ Materials The support materials used in the methods of this invention are preferably porous particulate materials, such as for c~ llpl~, talc, il~orgallic oxides, inorganic chlorides and resinous materia}s such as polyolefin or polymeric compounds.
The most p~rell~d support materials are porous inorganic oxide materials, 20 which include those from the Periodic Table of F.lem~nt~ of Groups 2, 3, 4, 5, 13 or 14 metal oxides. Silica, plllmin~ silica-~l~-min~ and mixtures thereof are particularly p, eLI l ed. Other inorg,dluc oxides that may be employed either alone or in co~ alion with the silica, ~IIImin~ or silica-~ min~ are ma$rle~ ;~ titania, ~,conia, and the like.
~ leîel~bly the support material is porous silica which has a surface area in the range of from 10 to 700 m2/g, a total pore volume in the range of from 0.1 to 4.0 cc/g and an average particle rli~meter in the range of from 10 to 500 llm.
More p.~fel~bly, the surface area is in the range of ~om 50 to 500 m2/g, the 30 pore volume is in the range of from 0.5 to 3.5 cc/g and the average particle tli~rnetçr is in the range of from 20 to 200 ~m. Most preferably the surface area W 0 98/13393 PCT~US97/14533 is in the range of ~om 100 to 400 m2/g, the pore volume is in the range of from 0.8 to 3.0 cc/g and the average particle fli~met~r is in the range of from 30 to100 ~m. The average pore di~meter oftypical porous support materials is in the range offrom 10 to 1000A. Preferably, a support material is used that has an S average pore di~nleter of from 50 to 500R, and most preferably ~om 75 to 3soA. It may be particularly desirable to dehydrate the silica at a te..lpe.~ re of from 1 00~C to 800~C anywhere from 3 to 24 hours.
Met~todfor Preparing the Catalyst Sysfem The methods of this invention are di~tin~ hed by the use of an aliphatic hydrocarbon solvent during the pl epa.alion of the catalyst system. Surprisingly, the reslllting catalyst systems have a markedly increased activity co.l.pared toconventionally prepared metallocene catalyst systems.
Preferably, the ratio of the total volume of aliphatic hydrocarbon to aromatic hydrocarbon used to prepal e the catalyst system is at least 1:1, more plcrel..bly in the range offrom 1:1 to 10:1 or more, even more l~lerel~bly from 2:1 to 8:1, even more preferably from 3:1 to 5:1.
Any aliphatic hydrocarbon or mixture of aliphatic hydrocarbons can be used in the methods ofthis invention. F'~,re.~bly the aliphatic hydrocarbon is aC3-Clo alkane. More p.t;re-~ly the aliphatic hydrocarbon is s~lected from the group concic~ing of pc~llanc, hexane, he~ e, isopclllane, cyclohexane, octane, 25 i~obut~ne, butane, and propane. Most p- ~rel ~bly the aliphatic hydrocarbon is selected ~om the group con~ of: isGpe.llanc, pentane, hexane, hcplane and isobutane.
Alumoxane is typically dissolved in toluene as a 10% to 30 % solution.
30 Preferably a 30% solution of alumoxane, pl crcl ~bly methyl~ll .mox~ne, is used to _, ~ .
minimi7e the volume ofto}uene. At higher alumoxane concentrations, gels tend to form.
The metallocene and ~ mo~ne may be independently contacted with the 5 support with either the metallocene or the alumoxane contacted first or the three components may be mixed together at one time. Likewise the aliphatic hydrocarbon solvent may be indepentlently contacted with the three components or with any combination of components. Thus the precipitation can occur either in the presence of the support, prior to contact with the support, or a~er one or lO more of the components are supported. Preferably, however, the metallocene and alumoxane are precGnlacted in an aromatic hydrocarbon solvent and their reactionproduct is mixed with the support. This is particularly prt;rw I ed when the metallocene alone is either insoluble or spa.ingly soluble in both aliphatic andaromatic hydrocalbons. It is also prer~,able to contact the metallocene and 15 alumoxane in solution, i.e., an aromatic hydrocarbon solution such as toluene.
The aliphatic hydrocarbon is preferably mixed with the support material and the metallocene/~ ..oxA~-e reaction product solution combined with the support at which point prtci,oilalion occurs.
In an alternative embodiment the total amount of alumoxane used to activate the metallocene is split into two portions which are appl o~ alely equal.
The first portion is reacted with the metallocene in solution to form a reactionproduct which is then mixed with a slurly of support material in aliphatic hydrocarbon. ~he second alumoxane portion is then added.
Regardless of which of the above methods is used, once all of the catalyst colllpol1cllls are coll~ ed, the ln".l~lre is easier to mix if a slurry is forrned. To f~çilit~te drying, however, it is preferable to use as little overall liquid as possible.
Thus, when using porous support material, it is pre~lled that the total volume of liquid (both aromatic and aliphatic hydrocarbon) applied to the support is less than 5 times the total pore volume of the porous support, more pl e~, dbly less than 4 times the total pore volume ofthe porous support and even more p-~rtlabl~ less than 3 times the total pore volume of the porous support. Procedures for measuring the total pore volume of porous support are well known in the art. Thep-ert;,l ~d method is described in Volume 1, Experimen~al Methods in Catalyst Rese.l, ~h, ~ dPmic Press, 1968, pages 67-96.
In pl ere" ed embodinlel-ls, the metallocene and activator are pr~colllacted and allowed to react in solution for a time period ranging from 1 minute to 16 hours, more prefe,ably at least 10 minl~tes, and most preferably 10 min-ltes to hour. Likewise, it is prere,dble to mix the metallocene/alumoxane reaction 10 product with a hexane slurry of support material and allow the mixture to sit for at least 10 min-ltes, p,e~el~ly 10 minlltes to one hour. If the alumoxane is split into portions, then again, it is preferable to allow the second portion to react with the metallocene/alumoxanelsupport material mixture for at least 10 minutçs, pre~rdbly 10 mimltes to 1 hour.
Once all of the co"ll)onents inrl~lding the aliphatic hydrocarbon are con~ ed, the catalyst system is p-c;rt;l ~bly dried although the catalyst system can be used directly in polyrnerization. If the catalyst system is dried or allowed to dry, preferably little or no heat is used. The exact drying conditions will depend 20 on the specific embodiment, the size of the catalyst batch, and the amount of liquid but in every in~t~nce it is plerel~ble to use little or no heat for the least amount of time possible. A vacuum or purge of inert gas such as nitrogen may be used but, again, it is preferable to use these sparingly to avoid co~ tion and reduction in catalyst activity.
The supported catalyst system may be used directly in polymerization or the catalyst system may be prepolyrnerized using methods well known in the art.
For details regarding prepolyl~ ion, see United States Patent Nos. 4,923,833 and 4,921,825, EP 0 279 863 and EP 0 354 893 each of which is fully 30 incorporated herein by l~r~le.lce.
. .
In an alternative embodiment, the catalyst system is prepaled using an olefin promoter as a metallocene reactant. This method has also has been found by the present inventor to lead to increased activity as described in copending U.S.
Patent Application No. ("Improved Metallocene Catalyst Systems" filed 5 on the same day as this application by the same inventor - fully i.,col~lo,~led herein by IGrG Gllce).
Polymerizal'ion and Ca~alyst System Performance The catalyst system prepaled by the methods ofthis invention may be used in the polymerization of any monomer and optionally comonomers in any process in~lu~ing gas, slurry or solution phase or high pressure autoclave processes. (As used herein, unless difrer~ te~l, "polymerization" in~ dçs copoly,..Gli,.~Lion and "mono",e." ineludes co-"ol1o,--er.) Preferably, a gas or slurry phase process is15 used, most p. c;re, ~Iy a bulk liquid propylene polylllcl i~dlion process is used.
In the prere" ed embodiment, this invention is directed toward the bulk liquid poly,..e. i~lion and copol~...el i~lion of propylene or ethylene, particularly propylene, in a slurry or gas phase poly..,e.i~dlion process, particularly a slurry 20 polymerization process. Another embodiment involves copolymerization reactions of propylene or ethylene, particularly propylene, with one or more ofthe alpha-olefin ,..onG."ers having from 4 to 20 carbon atoms, p,Gre,..bly 4-12 carbon atoms, for ex~ml le alpha-olefin comono,..e.~ of ethylene, butene-1, pentene-1, 4-methylpentene-1, hexene-l, octene-1, decene-1, and cyclic olefins such as styrene, cyclopentene or noll oll.~,ne. Other suitable monomers include polar vinyl, diolefins such as dienes, for e~l,?le, 1,3-b~lt~içne, 1,4-hexadiene, norborn~diçne or vi~,ylno,l,o~"~,ne, acetylene and aldehyde monomers.
In another embodiment ethylene or propylene is polymerized with at least - 30 two different comono",c~ to form a terpolymer and the like, the plGr~lled comonomers are a cG..lbhlation of alpha-olefin mono,.,G, ~ having 3 to 10 carbon CA 0226308l l999-02-0~
atoms, more prt;re- ~bly 3 to 8 carbon atoms, and/or dienes having 4 to 10 carbon atoms.
Typically in a gas phase polymerization process a continllous cycle is 5 employed where in one part of the cycle of a reactor, a cycling gas stream, otherwise known as a recycle stream or fluidizing medium, is heated in the reactor by the heat of polymerization. The recycle stream usually contains one or more monomers continuously cycled through a fl-lidi7ed bed in the plesence of a catalyst under reactive conditions. This heat is removed in another part of the 10 cycle by a cooling system external to the reactor The recycle stream is withdrawn from the fl.liAi7ed bed and recycled back into the reactor. Siml.lt~neously, polymer product is withdrawn from the reactor and new or fresh monomer is added to replace the polymerized monomer. (See for example U.S. Patent Nos. 4,543,399;
4,588,790; 5,028,670, 5,352,749; 5,405,922, and 5,436,304 all of which are fi-lly 15 incorporated herein by l ererellce.) A slurry poly-llc;l i~lion process generally uses pressures in the range of I
to 500 atmosphel es or even greater and tenll)e~ res in the range of -60~C to 280~C. In a slurry polymerization, a suspension of solid, particulate polymer is20 formed in a liquid polymerization me~i~-m to which ethylene and comonomers and often hydrogen along with catalyst are added. The liquid employed in the polymerization me(lium can be, for example, an alkane or a cyclo~lk~ne. The merlillm employed should be liquid under the conditions of polyme-i~;~lion and relatively inert. Non-limiting ~ ;'~,5 of liquid m~ lm~ include hexane and 25 isobutane.
As shown below by the E. ~ - l 'es, the catalyst systems of this invention exhibit markedly increased activity as cor-pa-~d to conventionally prepared supported metallocene catalyst systems. Any increase in activity is highly 30 desirable particularly in col~ .ial processes.
96B065.p~
The polymers and copolymers made by the catalyst systems of the invention are useful in forming operations such as, for example, film, sheet, and fiber extrusion and co-extrusion as well as blow molding, injection molding, sheet thermoforming and rotational molding. Films include blown or cast films in mono-5 layer or multilayer constructions formed by coextrusion or by l~min~tion Such films are useful as shrink film, cling film, stretch film, sealing films, oriented films, snack paçl~ging, heavy duty bags, grocery sacks, baked and frozen food p~ck~ging, medical pacl~gin~ industrial liners, membranes, etc in food-contact and non-food contact applications Fiber forming operations include melt spinning, 10 solution spinning and melt blown fiber operations Such fibers may be used in woven or nonwoven form to make filters, diaper fabrics, medical garments, " ~ . geotextiles, etc. Extruded articles in~ de, for example, medical tubing, wire and cable coatings, geomembranes, and pond liners Molded articles include single andmulti-layered constructions in the form of bottles, tanks, large hollow articles, 15 rigid food containers and toys, etc.
EXAMPLES
20 Example 1 10 g of silica gel (Davison D-948, Average Particle Size, "APS", = 35 m, dried at 600~C) was charged into an 226.8 g (8 oz) bottle equipped with a m~gnetiC stirring bar. 40 ml of hexane was added into the bottle. Into a 113.4 g25 (4 oz.) bottle equipped with a m~f~netic stirring bar, a 0.1 lg of rac-Me2Si(2-Me-4-phenylindenyl)2ZrC12 and 5 ml methylalumoxane ("MAO") in toluene solution (30wt%) were charged. The mixture was stirred at ambient tempel~ure for 10 minutes The mixture was then transferred into the 226.8 g (8 oz) bottle cont~ining the silica gel and hexane slurry. This mixture was allowed to react at 30 ambient temperature for 10 min~ltes 6.4 ml of MAO in toluene (30wt%) was charged into the bottle and the mixture was allowed to react at ambient AMENDED SHEET
96B065pa ', ';;
temperature for 10 minl~tes. At the end of the reaction, the mixture was dried by nitrogen purging at 40~C to 50~C. A free flowing solid was obtained at the end of the preparation.
Into a clean 2-liter autoclave, a 0.3 ml oftriethylal~1min~1m in heptane (1.5 M) followed by 1 liter of liquid propylene were charged. The reactor was heated to 70~C. lO0 mg ofthe cataiyst prepared above was then charged into the autoclave through a catalyst injection tube. The catalyst was washed into the autoclave by 200 ml of liquid propylene. The total pressure inside the reactor was ' 10 around 3309.6 kPa (480 psig). The polymerization was allowed to proceed at 70~C for 1 hour. After the polymerization, the unreacted propylene was vented and the polymer slurry was transferred into an evaporation dish. The autoclave inside wall and agitator were very clean. A total of 294g of polymer was obtained.
Example 2 Example 1 was repeated except that 0.2 g of rac- Me2Si(2-Me-4-phenylindenyl)2ZrCl2 was used in the p-epa ~lion. A total of 187 g of polymer was obtained.
. Example 3 Example 1 was repeated except that all 11.4 ml of MAO was mixed with 25 the metallocene at the be~inning and no subsequent MAO was added. A total of l 99g of polymer was obtained.
AMENOED SHEET
96B065 .pcl Example 4 Example 3 was repeated except that 0.2 g of rac- Me2Si(2-Me-4-phenylindenyl)2ZrC12 was used in the preparation . A total of 169g of polymer 5 was obtained.
Example 5 (Colnpala~ e) 10 g of silica gel (Davison D-948, Average Particle Size, "APS", = 35 m, dried at 600~C) was charged into an 226.8 g (8 oz) boKle equipped with a magnetic stirring bar. Into a 113.4 g (4 oz). bottle equipped with a magnetic ~ .
stirring bar, a 0.1 Ig of rac-Me2Si(2-Me-indenyl)2ZrC12 and 11.4 ml methylalumoxane ("MAO") in toluene solution (30wt%) were charged. The mixture was stirred at ambient temperature for 10 minl1tes. 30 ml oftoluene solvent was charged into the m~xture and the mixture was then transferred into the 226.8 g (8 oz) bottle con~ g the silica gel. This mixture was allowed to react at ambient tempclaL~lre for 10 minlltes 6.4 ml of MAO in toluene (30wt%) was charged into the bottle and the mixture was allowed to react at ambient ten.pe. a~llre for 10 minl~tes At the end of the reaction, the mixture was dried by nitrogen purging at 40~C to 50~C. A free flowing solid was obtained at the end of the ,~repa~tion. A total of 160 g of polymer was obtained following the - polymerization procedure of Example 1.
Example 6 10 g of silica gel (Davison D-948, Average Particle Size, "APS", = 35 m, dried at 600~C) was charged into an 226.8 g (8 oz) bottle equipped with a magnetic stirring bar. 40 ml of hexane was charged into the bottle. Into a 113.4 g (4 oz). bottle equipped with a magnetic stirring bar, a 0.2g of rac-Me2Si(2-Me-4-phenylindenyl)2ZrC12 and 11.4 ml methylalumoxane ("MAO") in toluene solution (30wt%) were charged. The mixture was stirred at ambient temperature for 10 AMENDED SHEET
96B065.~
minlltes The mixture was then transferred into the 226.8 g (8 oz) bottle cont~ining the silica gel and hexane slurry. This mixture was allowed to react at ambient temperature for 10 minlltes 0.5 ml of styrene (99%) was charged into the bottle and the mixture was allowed to react at ambient temperature for 10 minutes At the end of the reaction, the mixture was dried by nitrogen purging at40~C to 50~C. A free flowing solid was obtained at the end of the preparation. Atotal of 232 g of polymer was obtained following the polymerization procedure ofExample 1.
- lO Example 7 10 g of silica gel (Davison D-948, Average Particle Size, "APS", = 35 m, dried at 600~C) was charged into an 226.8 g (8 oz) bottle equipped with a magnetic stirring bar. 40 ml of hexane was added into the bottle. Into a 113.4 g(4 oz). bottle equipped with a magnetic stirring bar, a 0.2g of rac-Me2Si(2-Me-4-phenylindenyl)2ZrCl2 and 5 ml methylalumoxane ("MAO") in toluene solution (30wt%) were charged. The mixture was stirred at ambient temperature for 10 minlltes. The mixture was then transferred into the 226.8 g (8 oz) bottle cont~ining the silica gel and hexane slurry. This mixture was allowed to react at ambient temperature for 10 minutes 6.4 ml of MAO in toluene (30wt%) was charged into the bottle and the mixture was allowed to react at ambient ~ temperature for 10 mimltes. 0.5 ml of styrene (99%) was charged and the mixture was allowed to react at ambient temperature for 10 min~ltçs At the end ofthe reaction, the mixture was dried by nitrogen purging at 40~C to 50~C. A free flowing solid was obtained at the end of the preparation. A total of 240 g of polymer was obtained following the polymerization procedure of Example 1.
While the present invention has been described and illustrated by reference to particular embotlim~nts, it will be appreciated by those of ordinary skill in the art that the invention lends itself to many di~el ellt variations not illustrated herein. For these reasons, then, reference should be made solely to the 96B065.p~
appended claims for purposes of determining the true scope of the present invention.
Although the appendant claims have single appendencies in accordance 5 with U.S. patent practice, each of the features in any of the appendant claims can be combined with each of the features of other appendant claims or the main claim.
- ., Ai~JlENDED SHEET
to 500 atmosphel es or even greater and tenll)e~ res in the range of -60~C to 280~C. In a slurry polymerization, a suspension of solid, particulate polymer is20 formed in a liquid polymerization me~i~-m to which ethylene and comonomers and often hydrogen along with catalyst are added. The liquid employed in the polymerization me(lium can be, for example, an alkane or a cyclo~lk~ne. The merlillm employed should be liquid under the conditions of polyme-i~;~lion and relatively inert. Non-limiting ~ ;'~,5 of liquid m~ lm~ include hexane and 25 isobutane.
As shown below by the E. ~ - l 'es, the catalyst systems of this invention exhibit markedly increased activity as cor-pa-~d to conventionally prepared supported metallocene catalyst systems. Any increase in activity is highly 30 desirable particularly in col~ .ial processes.
96B065.p~
The polymers and copolymers made by the catalyst systems of the invention are useful in forming operations such as, for example, film, sheet, and fiber extrusion and co-extrusion as well as blow molding, injection molding, sheet thermoforming and rotational molding. Films include blown or cast films in mono-5 layer or multilayer constructions formed by coextrusion or by l~min~tion Such films are useful as shrink film, cling film, stretch film, sealing films, oriented films, snack paçl~ging, heavy duty bags, grocery sacks, baked and frozen food p~ck~ging, medical pacl~gin~ industrial liners, membranes, etc in food-contact and non-food contact applications Fiber forming operations include melt spinning, 10 solution spinning and melt blown fiber operations Such fibers may be used in woven or nonwoven form to make filters, diaper fabrics, medical garments, " ~ . geotextiles, etc. Extruded articles in~ de, for example, medical tubing, wire and cable coatings, geomembranes, and pond liners Molded articles include single andmulti-layered constructions in the form of bottles, tanks, large hollow articles, 15 rigid food containers and toys, etc.
EXAMPLES
20 Example 1 10 g of silica gel (Davison D-948, Average Particle Size, "APS", = 35 m, dried at 600~C) was charged into an 226.8 g (8 oz) bottle equipped with a m~gnetiC stirring bar. 40 ml of hexane was added into the bottle. Into a 113.4 g25 (4 oz.) bottle equipped with a m~f~netic stirring bar, a 0.1 lg of rac-Me2Si(2-Me-4-phenylindenyl)2ZrC12 and 5 ml methylalumoxane ("MAO") in toluene solution (30wt%) were charged. The mixture was stirred at ambient tempel~ure for 10 minutes The mixture was then transferred into the 226.8 g (8 oz) bottle cont~ining the silica gel and hexane slurry. This mixture was allowed to react at 30 ambient temperature for 10 min~ltes 6.4 ml of MAO in toluene (30wt%) was charged into the bottle and the mixture was allowed to react at ambient AMENDED SHEET
96B065pa ', ';;
temperature for 10 minl~tes. At the end of the reaction, the mixture was dried by nitrogen purging at 40~C to 50~C. A free flowing solid was obtained at the end of the preparation.
Into a clean 2-liter autoclave, a 0.3 ml oftriethylal~1min~1m in heptane (1.5 M) followed by 1 liter of liquid propylene were charged. The reactor was heated to 70~C. lO0 mg ofthe cataiyst prepared above was then charged into the autoclave through a catalyst injection tube. The catalyst was washed into the autoclave by 200 ml of liquid propylene. The total pressure inside the reactor was ' 10 around 3309.6 kPa (480 psig). The polymerization was allowed to proceed at 70~C for 1 hour. After the polymerization, the unreacted propylene was vented and the polymer slurry was transferred into an evaporation dish. The autoclave inside wall and agitator were very clean. A total of 294g of polymer was obtained.
Example 2 Example 1 was repeated except that 0.2 g of rac- Me2Si(2-Me-4-phenylindenyl)2ZrCl2 was used in the p-epa ~lion. A total of 187 g of polymer was obtained.
. Example 3 Example 1 was repeated except that all 11.4 ml of MAO was mixed with 25 the metallocene at the be~inning and no subsequent MAO was added. A total of l 99g of polymer was obtained.
AMENOED SHEET
96B065 .pcl Example 4 Example 3 was repeated except that 0.2 g of rac- Me2Si(2-Me-4-phenylindenyl)2ZrC12 was used in the preparation . A total of 169g of polymer 5 was obtained.
Example 5 (Colnpala~ e) 10 g of silica gel (Davison D-948, Average Particle Size, "APS", = 35 m, dried at 600~C) was charged into an 226.8 g (8 oz) boKle equipped with a magnetic stirring bar. Into a 113.4 g (4 oz). bottle equipped with a magnetic ~ .
stirring bar, a 0.1 Ig of rac-Me2Si(2-Me-indenyl)2ZrC12 and 11.4 ml methylalumoxane ("MAO") in toluene solution (30wt%) were charged. The mixture was stirred at ambient temperature for 10 minl1tes. 30 ml oftoluene solvent was charged into the m~xture and the mixture was then transferred into the 226.8 g (8 oz) bottle con~ g the silica gel. This mixture was allowed to react at ambient tempclaL~lre for 10 minlltes 6.4 ml of MAO in toluene (30wt%) was charged into the bottle and the mixture was allowed to react at ambient ten.pe. a~llre for 10 minl~tes At the end of the reaction, the mixture was dried by nitrogen purging at 40~C to 50~C. A free flowing solid was obtained at the end of the ,~repa~tion. A total of 160 g of polymer was obtained following the - polymerization procedure of Example 1.
Example 6 10 g of silica gel (Davison D-948, Average Particle Size, "APS", = 35 m, dried at 600~C) was charged into an 226.8 g (8 oz) bottle equipped with a magnetic stirring bar. 40 ml of hexane was charged into the bottle. Into a 113.4 g (4 oz). bottle equipped with a magnetic stirring bar, a 0.2g of rac-Me2Si(2-Me-4-phenylindenyl)2ZrC12 and 11.4 ml methylalumoxane ("MAO") in toluene solution (30wt%) were charged. The mixture was stirred at ambient temperature for 10 AMENDED SHEET
96B065.~
minlltes The mixture was then transferred into the 226.8 g (8 oz) bottle cont~ining the silica gel and hexane slurry. This mixture was allowed to react at ambient temperature for 10 minlltes 0.5 ml of styrene (99%) was charged into the bottle and the mixture was allowed to react at ambient temperature for 10 minutes At the end of the reaction, the mixture was dried by nitrogen purging at40~C to 50~C. A free flowing solid was obtained at the end of the preparation. Atotal of 232 g of polymer was obtained following the polymerization procedure ofExample 1.
- lO Example 7 10 g of silica gel (Davison D-948, Average Particle Size, "APS", = 35 m, dried at 600~C) was charged into an 226.8 g (8 oz) bottle equipped with a magnetic stirring bar. 40 ml of hexane was added into the bottle. Into a 113.4 g(4 oz). bottle equipped with a magnetic stirring bar, a 0.2g of rac-Me2Si(2-Me-4-phenylindenyl)2ZrCl2 and 5 ml methylalumoxane ("MAO") in toluene solution (30wt%) were charged. The mixture was stirred at ambient temperature for 10 minlltes. The mixture was then transferred into the 226.8 g (8 oz) bottle cont~ining the silica gel and hexane slurry. This mixture was allowed to react at ambient temperature for 10 minutes 6.4 ml of MAO in toluene (30wt%) was charged into the bottle and the mixture was allowed to react at ambient ~ temperature for 10 mimltes. 0.5 ml of styrene (99%) was charged and the mixture was allowed to react at ambient temperature for 10 min~ltçs At the end ofthe reaction, the mixture was dried by nitrogen purging at 40~C to 50~C. A free flowing solid was obtained at the end of the preparation. A total of 240 g of polymer was obtained following the polymerization procedure of Example 1.
While the present invention has been described and illustrated by reference to particular embotlim~nts, it will be appreciated by those of ordinary skill in the art that the invention lends itself to many di~el ellt variations not illustrated herein. For these reasons, then, reference should be made solely to the 96B065.p~
appended claims for purposes of determining the true scope of the present invention.
Although the appendant claims have single appendencies in accordance 5 with U.S. patent practice, each of the features in any of the appendant claims can be combined with each of the features of other appendant claims or the main claim.
- ., Ai~JlENDED SHEET
Claims (10)
- Claim 1. A method for forming a supported metallocene catalyst system comprising:
(a) reacting one or more metallocenes and an alumoxane activator in an aromatic hydrocarbon solvent to form a catalyst solution; and (b) mixing the catalyst solution with support material in the presence of aliphatic hydrocarbon. - Claim 2. A method for forming a supported metallocene catalyst system comprising:
(a) reacting metallocene and an alumoxane activator in an aromatic hydrocarbon solvent to form a catalyst solution;
(b) mixing aliphatic hydrocarbon with support material; and (c) combining the catalyst solution with the mixture. - Claim 3 A method for forming a supported metallocene catalyst system comprising:
(a) reacting metallocene and a first alumoxane portion in an aromatic hydrocarbon solvent to form a catalyst solution;
(b) combining aliphatic hydrocarbon and support material to form a mixture;
(c) combining the catalyst solution with the mixture; and then (d) adding a second alumoxane portion. - Claim 4. The method of any of the preceding claims wherein the ratio ofaliphatic hydrocarbon to aromatic hydrocarbon is at least 1:1.
- Claim 5 . The method of any of the preceding claims wherein the metallocene is represented by the formula:
wherein M is selected from the group consisting of titanium, zirconium, hafnium,vanadium niobium, tantalum, chromium, molybdenum and tungsten;
R1 and R2 are identical or different, are one of a hydrogen atom, a C1-C10 alkyl group, preferably a C1-C3 alkyl group, a C1-C10 alkoxy group, a C6-C10 aryl group, a C6-C10 aryloxy group, a C2-C10 alkenyl group, a C2-C4 alkenyl group, a C7-C40 arylalkyl group, a C7-C40 alkylaryl group, a C8-C40 arylalkenyl group, or a halogen atom;
R3 and R4 are hydrogen atoms;
R5 and R6 are identical or different, and are one of a halogen atom, a C1-C10 alkyl group which may be halogenated, a C6-C10 aryl group which may be halogenated, a C2-C10 alkenyl group, a C7-C40 -arylalkyl group, a C7-C40 alkylaryl group, a C8-C40 arylalkenyl group, a -NR2 15, -SR15, -OR15, -OSiR3 15 or -PR2 15 radical, wherein R15 is one of a halogen atom, a C1-C10 alkyl group, or a C6-C10 aryl group;
R7 is -B(R11), -A1(R11)-, -Ge-, -Sn-, -O-, -S-, -SO-, -SO2-, -N(R11), -CO-, -p(R11)-, or -P(O)(R11)-;
wherein:
R11, R12 and R13 are identical or different and are a hydrogen atom, a halogen atom, a C1-C20 alkyl group, a C1-C20 fluoroalkyl group, a C6-C30 aryl group, a C6-C30 fluoroaryl group, a C1-C20 alkoxy group, a C2-C20 alkenyl group, a C7-C40 arylalkyl group, a C8-C40 arylalkenyl group, a C7-C40 alkylaryl group, or R11 and R12, or R11 and R13, together with the atoms binding them, can form ring systems;
M2 is silicon, germanium or tin;
R8 and R9 are identical or different and have the meanings stated for R11;
m and n are identical or different and are zero, 1 or 2, m plus n being zero, 1 or 2; and the radicals R10 are identical or different and have the meanings stated for R11, R12 and R13 and two adjacent R10 radicals can be joined together to form a ring system. - Claim 6. The method of any of the preceding claims wherein the aliphatic hydrocarbon is a C3 to C10 alkane.
- Claim 7. The method of any of the preceding claims further comprising the step of recovering dry supported metallocene catalyst system.
- Claim 8. The method of any of the preceding claims wherein the aliphatic hydrocarbon is isopentane or hexane, the support material is silica and the activator is methylalumoxane.
- Claim 9. The method of any of the preceding claims wherein the metallocene is selected from the group consisting of rac-:
dimethylsilandiylbis(2-methylindenyl)zirconium dichloride;
dimethylsilandiylbis(2,4-dimethylindenyl)zirconium dichloride;
dimethylsilandiylbis(2,5,6-trimethylindenyl)zirconium dichloride;
dimethylsilandiylbis indenyl zirconium dichloride; dimethylsilandiylbis(4,5,6,7-tetrahydroindenyl)zilconium dichloride dimethylsilandiylbis(2-methyl-4,5-benzoindenyl)zirconium dichloride;
dimethylsilandiylbis(2-methyl-4-phenylindenyl)zirconium dichloride;
dimethylsilandiylbis(2-methyl-4,6-diisopropylindenyl)zirconium dichloride;
dimethylsilandiylbis(2-methyl-4-napthylindenyl)zirconium dichloride; and dimethylsilandiylbis(2-ethyl-4-phenylindenyl)zirconium dichloride. - 10. A metallocene catalyst system prepared by the method of any of the preceding claims.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US2664496P | 1996-09-24 | 1996-09-24 | |
| US60/026,644 | 1996-09-24 | ||
| PCT/US1997/014533 WO1998013393A1 (en) | 1996-09-24 | 1997-08-19 | Improved method for preparing supported metallocene catalyst systems |
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| JP (1) | JP2001500921A (en) |
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| CA (1) | CA2263081A1 (en) |
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| GB0017547D0 (en) * | 2000-07-17 | 2000-09-06 | Bp Chem Int Ltd | Supported polymerisation catalysts |
| US6720396B2 (en) | 2000-11-30 | 2004-04-13 | Univation Technologies, Llc | Polymerization process |
| US20020137861A1 (en) * | 2000-12-04 | 2002-09-26 | Woo Min Song | Polymerization process |
| JP5268087B2 (en) * | 2004-07-08 | 2013-08-21 | エクソンモービル・ケミカル・パテンツ・インク | Polymer production under supercritical conditions |
| MX2009004201A (en) * | 2006-10-19 | 2009-07-15 | Ct De Investigacion En Quimica | Catalyst for the heterogeneous phase polymerisation of conjugated dienes and olefins, method for obtaining same and use thereof. |
| CN112409515B (en) * | 2019-08-23 | 2023-10-20 | 中国石油化工股份有限公司 | Preparation method of metallocene polypropylene catalyst |
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| DE4119343A1 (en) * | 1991-06-12 | 1992-12-17 | Basf Ag | INSULATED, SUPPORTED CATALYST SYSTEM FOR THE POLYMERIZATION OF C (DOWN ARROW) 2 (DOWN ARROW) - TO C (DOWN ARROW) 1 (DOWN ARROW) (DOWN ARROW) 0 (DOWN ARROW) -ALK-1-END |
| FI112233B (en) * | 1992-04-01 | 2003-11-14 | Basell Polyolefine Gmbh | Catalyst for olefin polymerization, process for its preparation and its use |
| US5240894A (en) * | 1992-05-18 | 1993-08-31 | Exxon Chemical Patents Inc. | Method for making and using a supported metallocene catalyst system |
| CA2163789C (en) * | 1993-05-25 | 2006-10-24 | Terry John Burkhardt | Supported metallocene catalyst systems for the polymerization of olefins, preparation and use thereof |
| FI96866C (en) * | 1993-11-05 | 1996-09-10 | Borealis As | Support olefin polymerization catalyst, its preparation and use |
| AU685649B2 (en) * | 1994-06-24 | 1998-01-22 | Exxon Chemical Patents Inc. | Polymerization catalyst systems, their production and use |
| US5763543A (en) * | 1994-09-14 | 1998-06-09 | Exxon Chemical Patents Inc. | Olefin polymerization process with little or no scavenger present |
-
1997
- 1997-08-19 KR KR1019990702347A patent/KR20000048478A/en not_active Application Discontinuation
- 1997-08-19 WO PCT/US1997/014533 patent/WO1998013393A1/en not_active Application Discontinuation
- 1997-08-19 CA CA002263081A patent/CA2263081A1/en not_active Abandoned
- 1997-08-19 EP EP97936513A patent/EP0928297A1/en not_active Withdrawn
- 1997-08-19 JP JP10515637A patent/JP2001500921A/en active Pending
- 1997-08-19 CN CN97198171A patent/CN1231678A/en active Pending
- 1997-09-08 TW TW086112949A patent/TW367339B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| CN1231678A (en) | 1999-10-13 |
| EP0928297A1 (en) | 1999-07-14 |
| JP2001500921A (en) | 2001-01-23 |
| WO1998013393A1 (en) | 1998-04-02 |
| TW367339B (en) | 1999-08-21 |
| KR20000048478A (en) | 2000-07-25 |
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