Elastic polypropylenes and catalysts for their manufacture

A metallocene catalyst and an activating cocatalyst for olefin polymerization, said metallocene having the structure

• {ligand1-bridge-ligand2}MX2,
• wherein
• ligand1 and ligand2 are different and are selected from the group consisting of substituted and unsubstituted cyclopentadienyl, indenyl, fluorenyl, and cyclopentaphenanthryl ring groups, wherein, when present, ring group substituents are selected from the group consisting of
• i) C1-C4 straight-chain or branched alkyl,
• ii) C6-C20 aryl,
• iii) C7-C20 alkylaryl,
• iv) C4-C7 cycloalkyl
• v) (—CH2—)n or (—CH═CH—)m connecting adjacent or non-adjacent ring carbon atoms in the same ring structure, wherein n is 3, 4, or 5, or m=1, 2, 3, or 4,
• vi) fused aromatic rings, and
• vii) fused aromatic rings substituted by any one of groups i)-v);
• bridge is selected from the group consisting of
• i) >CR1R2
• ii) >SiR1R2
• iii) —CR1R2—CR3R4—
• iv) —SiR1R2—SiR3R4—
• v) —CR1R2—SiR3R4—
• vi) —SiR1R2—CR3R4—, wherein R1, R2, R3, and R4 can be the same or different and are selected from the group consisting of H, C1-C20 straight-chain or branched alkyl, C6-C20 aryl, and C3-C8 cycloalkyl;
• M is a metal atom selected from the group consisting of Zr, Hf, and Ti, and
• X is selected from the group consisting of Cl, Br, I, C1-C20 straight-chain or branched alkyl, C6-C20 aryl, C7-C20 alkylaryl, and C7-C20 arylalkyl,
• wherein the metallocene catalyst exhibits an asymmetry parameter of 1.30 to 1.69, with the proviso that when M=Zr, and bridge=C2H4, then component (v) is (—CH2—)n or (—CH═CH)m′, wherein n=3, 4, or 5 and m′ is 2, 3 or 4.

A composition of matter having a formula selected from the group consisting of

• H{flu-C2H4—H2CPA}H
• H{flu-C2H4-2-CH3-4,5-benzindene}H
• H{flu-SiR2-CPA}H
• H{flu-SiR2—H2CPA}H
• wherein R is a methyl or phenyl group.

A method of making chemical compounds having the formula

• H{ligand1-CH2CH2-ligand2}H
• wherein ligand1 and ligand2 are different and are selected from the group consisting of substituted and unsubstituted cyclopentadienyl, indenyl, fluorenyl, and cyclopentaphenanthrene ring groups, wherein, when present, ring group substituents are selected from the group consisting of
• i) C1-C4 straight-chain or branched alkyl,
• ii) C6-C20 aryl,
• iii) C7-C20 alkylaryl,
• iv) C4-C7 cycloalkyl
• v) (—CH2—)n or (—CH═CH—)m connecting to adjacent or non-adjacent ring carbon atoms in the same ring structure, wherein n is 3, 4, or 5, and m=1, 2, 3, or 4,
• vi) fused aromatic rings, and
• vii) fused aromatic rings substituted by any one of groups i)-v), comprising the steps:
• 1) deprotonating the hydroxyl group of a compound of the type
• H{ligand1-CH2CH2OH};
• 2) reacting the deprotonated compound with highly fluorinated alkyl sulfonyl fluoride to obtain a highly fluorinated alkyl sulfonate of the type
• H{ligand1-CH2CH2—OSO2Rf};
• wherein Rf is a straight chain, branched, or cyclic alkyl group containing 1 to 20 carbon atoms and optionally O, N, or S heteroatoms, with more than 50% of the H atoms being replaced by fluorine atoms;
• 3) condensing the trifluoromethanesulfonate with the conjugate base of a compound of the type
• ligand2-H.

A method of producing polypropylene in the presence of a metallocene catalyst and an activating cocatalyst, said metallocene, comprising contacting propylene with a catalyst having the structure

• {ligand1-bridge-ligand2}MX2,
• wherein
• ligand1 and ligand2 are different and are selected from the group consisting of substituted and unsubstituted cyclopentadienyl, indenyl, fluorenyl, and cyclopentaphenanthrene ring groups, wherein, when present, ring group substituents are selected from the group consisting of
• i) C1-C4 straight-chain or branched alkyl,
• ii) C6-C20 aryl,
• iii) C7-C20 alkylaryl,
• iv) C4-C7 cycloalkyl
• v) (—CH2—)n or (—CH═CH—)m connecting adjacent or non-adjacent ring carbon atoms in the same ring structure, wherein n is 3, 4, or 5, and m=1, 2, 3, or 4,
• vi) fused aromatic rings, and
• vii) fused aromatic rings substituted by any one of groups i)-v);
• bridge is selected from the group consisting of
• i) >CR1R2
• ii) >SiR1R2
• iii) —CR1R2—CR3R4—
• iv) —SiR1R2—SiR3R4—
• v) —CR1R2—SiR3R4—
• vi) —SiR1R2—CR3R4—, wherein R1, R2, R3, and R4 can be the same or different and are selected from the group consisting of H, C1-C20 straight-chain or branched alkyl, C6-C20 aryl, and C3-C8 cycloalkyl;
• M is a metal atom selected from the group consisting of Zr, Hf, and Ti, and
• X is selected from the group consisting of Cl, Br, I, C1-C20 straight-chain or branched alkyl, C6-C20 aryl, C7-C20 alkylaryl, and C7-C20 arylalkyl,
• wherein the metallocene catalyst exhibits an asymmetry parameter of 1.03 to 1.69.

A propylene copolymer, said copolymer being elastomeric and being soluble in at least one nonpolar organic solvent selected from the group consisting of toluene, xylene, heptane, and hexane, said polymer comprising

• a) greater than 3 weight percent and up to 45 weight percent homotactic sequences each having only r or m diads, all of which homotactic sequences have a helical length in the range of 20 to 150 Å, and
• b) in the range of 55 to 97 weight percent of the total composition being the sum of
• 1) homotactic sequences, each having only r or m diads, and being less than 20 Å in helical length, and
• 2) heterotactic sequences having unequal numbers of r and m diads,
• said polymer having a molecular weight (Mw) of at least 35,000.