Method of controlling polymer architecture

A continuous process to copolymerize ethylene and at least one co-monomer using a dual catalyst to provide a polymer composition comprising a first polymer component and a second polymer component wherein said continuous process comprises:

• controlling the ratio of said first polymer component to said second polymer component by conducting said process in the presence of between 0 molar ppm and 500 molar ppm of carbon dioxide;
• wherein lowering the level of carbon dioxide in molar ppm from a first higher level to a second lower level, decreases said ratio of said first polymer component to said second polymer component, and raising the level of carbon dioxide in molar ppm from a first lower level to a second higher level, increases said ratio of said first polymer component to said second polymer component;
• provided that said dual catalyst comprises:
• a chromium catalyst,
• a group 4 single site catalyst,
• one or more catalyst activators,
• and a support;
• wherein said chromium catalyst provides said first polymer component and said group 4 single site catalyst provides said second polymer component;
• and wherein said group 4 single site catalyst has the formula:
• Cp(PI)MX2
• where Cp is a cyclopentadienyl type ligand, PI is a phosphinimide ligand, M is Ti, Zr or Hf, and each X independently, is an activatable ligand.

A process to polymerize ethylene and optionally a co-monomer with a combination catalyst, said process providing a polymer composition comprising a first polymer component and a second polymer component;

• wherein an activity modifier is contacted with said combination catalyst in an amount sufficient to change the ratio of said first polymer component to said second polymer component;
• wherein said combination catalyst comprises:
• a chromium catalyst,
• a group 4 single site catalyst,
• and one or more catalyst activators,
• further provided that said chromium catalyst is less sensitive to said activity modifier in terms of lost activity than said group 4 single site catalyst;
• and wherein said group 4 single site catalyst has the formula:
• Cp(PI)MX2
• where Cp is a cyclopentadienyl type ligand, PI is a phosphinimide ligand, M is Ti, Zr or Hf, and each X independently, is an activatable ligand.

A process to co-polymerize ethylene and at least one co-monomer using a combination catalyst to provide a polymer composition comprising a first polymer component and a second polymer component, wherein the process comprises:

• controlling the ratio of the first polymer component to the second polymer component by altering the amount of carbon dioxide present in a polymerization zone;
• wherein the combination catalyst comprises:
• a chromium catalyst, a group 4 single site catalyst, one or more catalyst activators, and one or more support;
• and
• wherein the chromium catalyst is less sensitive to carbon dioxide in terms of reduced activity than the group 4 single site catalyst and provides the first polymer component;
• and
• the group 4 single site catalyst is more sensitive to carbon dioxide in terms of reduced activity than the chromium catalyst and provides the second polymer component;
• and wherein said group 4 single site catalyst has the formula:
• Cp(PI)MX2
• where Cp is a cyclopentadienyl type ligand, PI is a phosphinimide ligand, M is Ti, Zr or Hf, and each X independently, is an activatable ligand.