Polymerization processes for broadened molecular weight distribution
AssigneeExxonMobil Research and Engineering Company
InventorsGabor Kiss, Robert Patrick Reynolds, Jr., John W. Chu, Patrick Brant, James Richardson Lattner
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Abstract
Provided are methods of producing polymers with broadened molecular weight and/or composition distribution in a continuous homogeneous polymerization system utilizing reactor temperature gradients, reactor polymer concentration gradients, monomer concentration gradients, catalyst concentration gradients, and combinations thereof in the polymerization reactor. Such methods are particularly suitable when utilizing metallocene catalysts and other single-site catalysts, which generally produce polymers with narrow molecular weight and composition distribution.
Claims11
A continuous process for producing polymers in a homogeneous polymerization system, comprising:
- (a) providing a tubular, a loop or a stirred tank reactor with two or more feed entry ports;
- (b) feeding to the reactor through the two or more feed entry ports two or more reactor feed streams with the two or more reactor feed streams comprising:
- 1) two or more monomers;
- 2) one or more catalyst systems;
- 3) optional one or more scavengers;
- 4) optional one or more diluents or solvents;
- and 5) combinations thereof;
- wherein the reactor is at a temperature above the solid-fluid phase-transition temperature of the polymerization system and a pressure no lower than 10 MPa below the cloud point pressure of the polymerization system and less than 1500 MPa;
- wherein the polymerization system for the reactor is in its dense fluid state and comprises the two or more monomers, any diluent or solvent present, any scavenger present, and the polymer product;
- wherein the one or more catalyst systems comprise one or more catalyst precursors, one or more catalyst activators, and optionally, one or more catalyst supports, wherein the one or more catalyst precursors are chosen from metallocene catalysts, non-metallocene metal-centered, heteroaryl ligand catalysts, and late transition metal catalysts;
- wherein at least one of the monomers is ted to the reactor at an upstream feed entry port and at least one of the monomers is fed to the reactor at one or more downstream feed entry ports;
- wherein the total number of monomers fed to the reactor through the upstream feed entry port is less than the total number of monomers fed to the reactor through the upstream feed entry port and the one or more downstream feed entry ports;
- and
- (c) forming a polymer reactor effluent including a homogeneous fluid phase polymer-monomer mixture in the reactor;
- wherein the concentration of at least one monomer in the polymerization system in a first reactor zone in a baffled reactor or at 5% downstream of the reactor length from the upstream feed entry port of a baffle-free reactor is at least 5% different from the concentration of the same at least one monomer in the polymerization system at the one or more downstream feed entry ports;
- and
- wherein the Mw/Mn of the polymer product is greater than 2.3.
Dependencies are inferred from the claim text.