Methods of controlling ziegler-natta pre-catalyst particles formation and use for olefin polymerization
AssigneeBraskem America, Inc.
InventorsJonas Alves Fernandes, George S. Ostace, Dana Hess
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Abstract
A colloidal suspension includes an organic phase and a complex of Formula I as precursor for Ziegler-Natta catalyst synthesis: XTiClp(OR1)4-p.YMg(OR2)q(OR3)t (I). In Formula I, a molar ratio of X to Y (X/Y) is from 0.2 to 5.0, p is 0 or 1, 0<q<2, 0<t<2, the sum of q and t is 2, R1, R2, and R3 are each independently a linear or branched alkyl, a linear or branched heteroalkyl, a cycloalkyl, a substituted cycloalkyl, a substituted heterocycloalkyl, a substituted aryl, or a (heteroaryl)alkyl; and R2 is not the same as R3.
Claims18
A method of preparing a solid pre-catalyst system, the method comprising:
- in a reactor under agitation with a stirring mechanism, reacting a colloidal suspension of an organic solvent and a complex of Formula I with a halogenated compound or a mixture of halogenated compounds at a starting reactor temperature;
- allowing the colloidal suspension to react exothermically under a controlled feed rate to form a precipitate, which is then allowed to reach an upper temperature limit for a sufficient period of time to form a reacted colloidal suspension;
- and
- allowing the reacted colloidal suspension to cool to completion temperature;
- wherein:
- the complex of Formula I is:
- XTiClp(OR1)4-p·YMg(OR2)q(OR3)t (I)
- a molar ratio of X to Y (X/Y) is from 0.2 to 5.0;
- p is 0 or 1;
- 0<q<2;
- 0<t<2;
- the sum of q and t is 2;
- R1, R2, and R3 are each independently a linear or branched alkyl, a linear or branched heteroalkyl, a cycloalkyl, a substituted cycloalkyl, a substituted heterocycloalkyl, a substituted aryl, or a (heteroaryl)alkyl;
- R2 is not the same as R3;
- and
- the precipitate exhibits a D50 from about 3 μm to about 10 μm.
A solid pre-catalyst system comprising solid particles of a reaction product of a complex of Formula I with a halogenated compound or a mixture of halogenated compounds;
- wherein:
- XTiClp(OR1)4-p·YMg(OR2)q(OR3)t (I)
- a molar ratio of X to Y (X/Y) is from 0.2 to 5.0;
- p is 0 or 1;
- 0<q<2;
- 0<t<2;
- the sum of q and t is 2;
- R1, R2, and R3 are each independently a linear or branched alkyl, a linear or branched heteroalkyl, a cycloalkyl, a substituted cycloalkyl, a substituted heterocycloalkyl, a substituted aryl, or a (heteroaryl)alkyl;
- R2 is not the same as R3;
- and
- the solid particles exhibit a D50 from about 3 μm to about 12 μm.
A method of polymerizing or co-polymerizing olefin monomers, the method comprising:
- contacting a solid pre-catalyst system comprising solid particles of a composite of a reaction product of a halogenated compound and a colloidal suspension of a complex of Formula I with a reducing agent, optionally a chain transfer agent, and the olefin monomers:
- XTiClp(OR1)4-p·YMg(OR2)q(OR3)t (I)
- wherein:
- a molar ratio of X to Y (X/Y) is from 0.2 to 5.0;
- p is 0 or 1;
- 0<q<2;
- 0<t<2;
- the sum of q and t is 2;
- R1, R2, and R3 are each independently a linear or branched alkyl, a linear or branched heteroalkyl, a cycloalkyl, a substituted cycloalkyl, a substituted heterocycloalkyl, a substituted aryl, or a (heteroaryl)alkyl;
- R2 is not the same as R3;
- and
- the solid particles exhibit a D50 from about 3 μm to about 12 μm.
Dependencies are inferred from the claim text.