Spray dried, filled metallocene catalyst composition for use in polyolefin manufacture

• US 5,674,795 A
• Filed: 06/07/1995
• Issued: 10/07/1997
• Est. Priority Date: 12/23/1993
• Status: Expired due to Term

• Current Assignee: Union Carbide Chemicals & Plastics Technology Corporation (Dow, Inc.)
• Original Assignee: Union Carbide Chemicals & Plastics Technology Corporation (Dow, Inc.)
• Inventors: Smale, Mark Wilton, Lynn, Timothy Roger, Karol, Frederick John, Brady, Robert Converse III, Wasserman, Eric Paul
• Primary Examiner(s): WU, DAVID WEI HSIUNG
• Application Number:
  US08/486,412
• Time in Patent Office: 853 Days
• Field of Search: 502/9, 502/104, 502/117, 502/152, 526/160, 526/943
• US Class Current: 502/9
• CPC Class Codes: C08F 10/00 Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 2/44 Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• CPC Class Codes: C08F 210/14 Monomers containing five or more carbon atoms
• CPC Class Codes: C08F 210/16 Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 2500/12 Melt flow index or melt flow ratio
• CPC Class Codes: C08F 2500/18 Bulk density
• CPC Class Codes: C08F 2500/24 Polymer with special particle form or size
• CPC Class Codes: C08F 4/61912 in combination with an organoaluminium compound
• CPC Class Codes: C08F 4/61916 supported on a carrier, e.g. silica, MgCl2, polymer
• CPC Class Codes: C08F 4/61922 containing at least two cyclopentadienyl rings, fused or not
• CPC Class Codes: C08F 4/65912 in combination with an organoaluminium compound
• CPC Class Codes: C08F 4/65916 supported on a carrier, e.g. silica, MgCl2, polymer
• CPC Class Codes: C08F 4/6592 containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
• CPC Class Codes: C08F 4/65927 two cyclopentadienyl rings being mutually bridged
• CPC Class Codes: Y10S 526/943 Polymerization with metallocene catalysts

Abstract

Metallocene-containing catalyst compositions that include inert filler, a method for their preparation, and a method for their use in production of polyolefins are disclosed and claimed. The catalyst compositions contain solid particles of a mixture comprising a) a metallocene catalyst; b) a cocatalyst capable of activating said metallocene catalyst; and c) particulate filler material having an average particle size of less than about 10 micrometers that is unreactive with the metallocene catalyst and the cocatalyst. They are prepared by spray drying a slurry of the constituents.

Claims

1. A method of preparing a spray dried catalyst composition, comprising:

forming a suspension comprising;

a) a metallocene catalyst;

b) a cocatalyst capable of activating the metallocene catalyst; and

c) particulate filler material having an average particle size of 0.001 to 0.1 micrometers that is unreactive with the metallocene catalyst and the cocatalyst, in a diluent; and

spray drying the suspension to obtain the catalyst composition having an average particle size of 5 to 500 micrometers.

2. The method of claim 1, wherein the metallocene catalyst is an organometallic compound containing at least one cyclopentadienyl group bonded to a Group IIIB to VIII metal of the Periodic Table.

3. The method of claim 2, wherein the metallocene catalyst has the formula:

space="preserve" listing-type="equation">(C.sub.5 R.sub.n).sub.y R'"'"'.sub.z (C.sub.5 R.sub.m)MY.sub.(x-y-1)

wherein M is a metal from Groups IIIB to VIII of the Periodic Table;

(C₅ R_n) and (C₅ R_m) are independently cyclopentadienyl or substituted cyclopentadienyl groups bonded to M;

each R is independently a hydrogen alkyl, alkenyl, aryl, alkylaryl, or arylalkyl radical containing from 1 to 20 carbon atoms, or two carbon atoms are joined together to form a C₄ -C₆ ring;

each R'"'"' is a C₁ -C₄ substituted or unsubstituted alkylene radical, a dialkyl or diaryl germanium or silicon, or an alkyl or aryl phosphine or amine radical bridging (C₅ R_n) and (C₅ R_m) rings;

each Y is independently an aryl, alkyl, alkenyl, alkylaryl, or arylalkyl radical having from 1-20 carbon atoms, hydrocarboxy radical having from 1-20 carbon atoms, or halogen;

n and m are each 0, 1, 2, 3, or 4;

z is 0 or 1, and z is 0 when y is 0;

y is 0, 1, or 2;

x is 1, 2, 3, or 4 depending upon the valence state of M; and

x-y≧

1.

4. The method of claim 2, wherein the metallocene catalyst is a bridged metallocene having the formula:

##STR5## wherein;

Q is a bridging linkage selected from the group consisting of

space="preserve" listing-type="equation">R".sub.2 C<

, R".sub.2 Si<

, R".sub.2 Ge<

, and --C.sub.2 R".sub.4 --

wherein each R" moiety is independently H or an alkyl group, or two R" moieties are joined to form a ring;

each R moiety is independently an alkyl, cycloalkyl, alkenyl, cycloalkenyl, phenyl, alkyl-substituted phenyl, or a phenyl-substituted alkyl group, or two adjacent R groups on a given ring are joined to form a ring;

m is 0, 1, 2, 3, or 4;

n is 0, 1, 2, 3, or 4;

M is a Ti, Zr, or Hf atom; and

each Y'"'"' is independently H, an alkyl group, or a halogen atom.

5. The method of claim 1, wherein the metallocene catalyst is a constrained geometry metallocene comprising a metal atom of Groups IIIB to VIII, or the Lanthanide series and a delocalized π

-bonded moiety substituted with a constrain-inducing moiety, said complex having a constrained geometry about the metal atom such that the angle at the metal atom between the centroid of the delocalized, substituted π

-bonded moiety and the center of at least one remaining substituent is less than such angle in a similar complex containing a similar π

-bonded moiety lacking in such constrain-containing a similar π

-bonded moiety lacking in such constrain-inducing moiety, and provided further that for such complexes comprising more than one delocalized, substituted π

-bonded moiety, only one thereof for each metal atom of the complex is a cyclic, delocalized, substituted π

-bonded moiety.