Manufacture of stereoregular polymers

• US 6,211,310 B1
• Filed: 12/04/1998
• Issued: 04/03/2001
• Est. Priority Date: 06/05/1997
• 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: Goode, Mark Gregory, Lynn, Timothy Roger, Moffett, Jody Michael, Williams, Clark Curtis, Brady, Robert Converse III
• Primary Examiner(s): Wu, David W.
• Assistant Examiner(s): HARLAN, ROBERT D
• Application Number:
  US09/194,988
• Time in Patent Office: 851 Days
• Field of Search: 526/160, 526/901, 526/348, 526/68, 526/69, 526/70, 526/62, 526/66, 526/943, 526/904, 526/351
• US Class Current: 526/88
• CPC Class Codes: B01J 19/26 Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
• CPC Class Codes: B01J 2208/00017 Controlling the temperature
• CPC Class Codes: B01J 2208/00539 Pressure
• CPC Class Codes: B01J 2208/00752 Feeding
• CPC Class Codes: B01J 8/004 by means of a nozzle
• CPC Class Codes: B01J 8/1827 the fluidising gas being a reactant
• 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 210/06 Propene
• CPC Class Codes: C08F 210/08 Butenes
• 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 2500/15 Isotactic
• CPC Class Codes: C08F 4/65912 in combination with an organoaluminium compound
• 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 526/901 Monomer polymerized in vapor state in presence of transition metal containing catalyst
• CPC Class Codes: Y10S 526/943 Polymerization with metallocene catalysts

Abstract

The present invention teaches the use of particular soluble metallocene catalysts to produce stereoregular polymers in gas phase polymerizations wherein the catalysts are fed into a particular lean zone in the reactor. The metallocene catalysts are bridged bis(substituted indenyl) compounds.

Claims

1. A process for making stereoregular or regioregular polymers comprising feeding an unsupported metallocene catalyst and a cocatalyst in liquid form to a gas phase reactor in a resin lean particle zone within the reactor without immediately contacting growing polymer particles in the reactor to provide an average particle size ranging from about 0.025 to about 0.15 cm (about 0.01 to about 0.06 inches), wherein the metallocene is represented by the formula:

2. A process according to claim 1 wherein the cocatalyst is selected from the group consisting of:

(a) oligomeric linear alkyl aluminoxanes represented by the formula;

or (b) oligomeric cyclic alkyl aluminoxanes of the formula;

 

wherein s is 1-40, p is 3-40 and R*** is an alkyl group containing 1 to 12 carbon atoms.

3. A process according to claim 2 wherein s is 10-20.

4. A process according to claim 1 wherein isotactic polypropylene having xylene solubles of less than about 7% is made.

5. A process according to claim 1 wherein a polypropylene impact copolymer is made.

6. A process according to claim 1 wherein a propylene-butene random copolymer is made.

7. The process of claim 1 wherein the liquid catalyst in the carrier gas is introduced at a velocity ranging from about 15 m/s (about 50 ft/s) to the sonic velocity of said gas;

the particle-deflecting gas is introduced at a velocity ranging from about 3 m/s (about 10 ft/s) to about the sonic velocity of said gas; and

the tip-cleaning gas ranges in velocity from about 15 m/s (about 50 ft/s) to about the sonic velocity of said gas.

8. The process of claim 1 wherein the particle-deflecting gas and the tip-cleaning gas is about 69 to about 345 KPa gauge (about 10 to about 50 psig) higher in pressure than the gas in the reactor.

9. The process of claim 1 wherein the particle-deflecting gas is recycle gas and the tip-cleaning gas is monomer gas.

10. The process of claim 1 wherein the liquid catalyst is introduced by a catalyst delivery system comprising (i) a particle-deflecting gas tube enclosing a catalyst injection tube or nozzle or (ii) a particle-deflecting gas tube enclosing a tip-cleaning gas tube which in turn encloses a catalyst injection tube or nozzle.