Synthesis of metallocene polymerization catalyst
AssigneeNOVA Chemicals (International) S.A.
InventorsCharles Carter, Janelle Smiley-Wiens
Life of this patent
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Abstract
A one pot synthetic method for making a bridged cyclopentadienyl/fluorenyl type ligand and the corresponding ansa metallocene polymerization catalyst. In a key step, a cyclopentadienide/fluorenide dianion is prepared by combining a fluorene compound, a fulvene compound, and at least 2 molar equivalents of KN(SiMe3)2 in any order in the presence of an ether solvent under ambient conditions. Reaction of the cyclopentadienide/fluorenide dianion with a Group IV transition metal chloride, followed by alkylation gives a metallocene polymerization catalyst in good yields.
Claims13
A method for making a metallocene (II-Cl2) having the structure,
- the method comprising forming a compound (I) having the structure,
- by combining in a single reaction vessel containing an ether solvent, compounds (i) and (11):
- and
- with at least 2 molar equivalents of a metal salt of bis(trimethylsilyl)amide of the formula [M+][N(SiMe3)2−] per total number of moles of the compounds (i) and (ii);
- to give compound (I);
- and
- reacting in the same reaction vessel compound (I) with a Group IV transition metal chloride of the formula M*Cl4;
- wherein:
- the method is a one pot method;
- R1 and R2 are independently an unsubstituted or substituted alkyl, aryl, or alkenyl group;
- R3 is hydrogen, or an unsubstituted or substituted alkyl, aryl, or alkenyl group, or a substituted silyl group;
- R4A and R4B are independently a hydrocarbyl group, or hydrogen;
- M+ is Li+, Na+, or K+;
- and
- M* is Ti, Zr, or Hf.
A method for making a metallocene (II-R52) having the structure,
- the method comprising:
- forming a compound (I) having the structure,
- by combining in a single reaction vessel containing an ether solvent, compounds (i) and (ii):
- and
- with at least 2 molar equivalents of a metal salt of bis(trimethylsilyl)amide of the formula [M+][N(SiMe3)2−] per total number of moles of the compounds (i) and (ii);
- to give compound (I);
- and
- reacting in the same reaction vessel compound (I) with a Group IV transition metal chloride of the formula M*Cl4 to produce a metallocene (II-Cl2) having the structure,
- and
- in the same reaction vessel reacting the metallocene (II-Cl2) with at least 2 molar equivalents of an alkylating reagent selected from the group consisting of R5Li and R5MgBr;
- wherein:
- the method is a one pot method;
- R1 and R2 are independently an unsubstituted or substituted alkyl, aryl, or alkenyl group;
- R3 is hydrogen, or an unsubstituted or substituted alkyl, aryl, or alkenyl group, or a substituted silyl group;
- R4A and R4B are independently a hydrocarbyl group, or hydrogen;
- R5 is a methyl, or a benzyl group;
- M+ is Li+, Na+, or K+;
- and
- M* is Ti, Zr, or Hf.
Dependencies are inferred from the claim text.