Mixed catalyst system

• US 6,069,213 A
• Filed: 12/16/1997
• Issued: 05/30/2000
• Est. Priority Date: 12/16/1997
• Status: Expired due to Fees

• Current Assignee: Union Carbide Chemicals & Plastics Technology Corporation (Dow, Inc.)
• Original Assignee: Union Carbide Chemicals & Plastics Technology Corporation (Dow, Inc.)
• Inventors: Nemzek, Thomas Lloyd, Kao, Sun-Chueh, Karol, Frederick John, Brady, Robert Converse III
• Primary Examiner(s): Wu, David W.
• Assistant Examiner(s): Rabago, Roberto
• Application Number:
  US08/991,688
• Time in Patent Office: 896 Days
• Field of Search: 502/117, 502/118, 502/152, 502/113, 526/113, 526/114, 526/118, 526/119, 526/160, 526/161, 526/172, 526/943
• US Class Current: 526/113
• 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 10/02 Ethene
• CPC Class Codes: C08F 2/34 Polymerisation in gaseous state
• 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 2500/03 Narrow molecular weight distribution, i.e. Mw/Mn < 3
• CPC Class Codes: C08F 4/65904 in combination with another component of C08F4/64
• 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 4/65925 two cyclopentadienyl rings being mutually non-bridged
• CPC Class Codes: C08F 4/65927 two cyclopentadienyl rings being mutually bridged
• CPC Class Codes: Y10S 526/943 Polymerization with metallocene catalysts

Abstract

It has been found that the use of at least one unsupported metallocene polymerization catalyst with at least one supported metallocene polymerization catalyst in the polymerization of olefins allows for better control of the polymerization, especially gas phase polymerization. Such a system takes advantage of the high activity of the unsupported catalyst and the stability of a supported catalyst. Additionally, the relative timing of the addition of the supported and unsupported catalysts to a reaction system can be used to control a continuous polymerization reaction by stabilizing the reactor bed with the supported catalyst prior to addition of the unsupported catalyst.

Claims

1. A composition comprising an unsupported metallocene catalyst and a supported metallocene catalyst wherein both the unsupported and supported metallocene catalyst satisfy at least one of the following structural formulae (II) or (III):

##STR7## wherein;

M is a Hf or Zr metal;

L is a substituted or unsubstituted, π

-bonded ligand coordinated to M;

each Q is independently selected from the group consisting of --O--,--NR³ --, --CR³₂ --and --S--;

Y is C;

Z is selected from the group consisting of --OR³, --NR³₂, --CR³₃, --SR³, --SiR³₃, --PR³₂, and --H, with the proviso that when Q is --NR³ -- then Z is selected from the group consisting of --OR³, --NR³₂, --SR³, --SiR³₃, --PR³₂, and --H;

n is 1 or 2;

A is a univalent anionic group when n is 2 or A is a divalent anionic group when n is 1; and

each R³ is independently a group containing carbon, silicon, nitrogen, oxygen, and/or phosphorus and one or more R³ groups may be attached to the L substituent;

T is a bridging group selected from the group consisting of alkylene groups containing from 1 to 10 carbon atoms optionally substituted with carbon or heteroatoms, arylene groups containing from 1 to 10 carbon atoms optionally substituted with carbon or heteroatoms, germanium, silicone and alkyl phosphine; and

m is 1 to 7.

2. The composition according to claim 1, wherein L is a substituted cycloalkadienyl ligand, Q is O, Z is selected from the group consisting of --OR³, --CR³₃ and --NR³₂, A is a carbamate, carboxylate or other heteroallyl moiety defined by the combination of Q, Y and Z, R³ is selected from the group consisting of an alkyl, cycloalkyl and aryl group, and m is 2 or 3.

3. A process for polymerizing at least one olefin comprising polymerizing said at least one olefin in the presence of the catalyst composition of claim 1.

4. A process according to claim 3, where the at least one olefin is propylene.