Ethylene copolymerization process

A process for the preparation of ethylene copolymers comprising contacting under solution polymerization conditions,

• ethylene,
• one or more α-olefin(s),
• one or more diene(s), and
• a catalyst composition prepared from
• (a) alumoxane, and
• (b) at least one bis(cyclopentadienyl) zirconium compound having the following structure:
• where
• (i) Cp1 is an unsubstituted cyclopentadienyl ring,
• (ii) the substituted fluorenyl ring has at least two, non-hydrogen radical substituents, R1, independently selected from:
• hydrogen radical,
• unsubstituted hydrocarbyl, silyl, or germyl radicals having from 1-20 carbon, silicon or germanium atoms,
• substituted hydrocarbyl, silyl or germyl radicals having from 1-20 carbon, silicon or germanium atoms, in which one or more hydrogen atoms is replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical, an aryloxy radical or any other radical containing a Lewis acidic or basic functionality,
• C1-C20 hydrocarbyl-substituted, Ge-, Sn-, or Pb-metalloid radicals,
• halogen radicals,
• amido radicals,
• phosphido radicals,
• alkoxy radicals, and
• alkylborido radicals;
• and optionally, at least two R1 groups are joined together to form, along with the carbon atoms to which they are attached, a C4-C20 ring structure, which is saturated or partially saturated, and substituted or unsubstituted, the optional ring-structure substitution being selected from one or more R1 groups as defined under (ii) above;
• (iii) X is selected from C, Si, Ge, Sn or Pb;
• (iv) m=1,
• (v) Y is selected from hydrocarbyl radicals, hydrosilyl radicals, and hydrogermyl radicals;
• and
• (vi) R2 is selected from, unsubstituted C1-C20 hydrocarbyl, C1-C20 hydrocarbyl substituted with at least one Si, or C1-C20 hydrocarbyl substituted with at least one Ge;
• (vii) Q1 and Q2 are non-cyclopentadienyl radicals in which, independently, each Q is selected from halide, hydride, unsubstituted C1-C20 hydrocarbyl, C1-C20 hydrocarbyl substituted with at least one R1 group as defined under (ii) above, alkoxide, aryloxide, amide, halide, or phosphide;
• and optionally together Q1 and Q2 may form an alkylidene, cyclometallated hydrocarbyl, or any other divalent anionic chelating ligand.

A process for the preparation of ethylene copolymers with a density below 0.915 g/ml, comprising contacting under solution polymerization conditions,

• ethylene,
• one or more α-olefin(s),
• optionally one or more diene(s), and
• a catalyst composition prepared from
• a cocatalyst, and
• at least one bis(cyclopentadienyl) zirconium compound having the following structure:
• where
• (i) Cp1 is an unsubstituted cyclopentadienyl ring,
• (ii) the substituted cyclopentadienyl ring has at least two non-hydrogen radical substituents, R1, each independently selected from:
• hydrogen radical,
• unsubstituted hydrocarbyl, silyl or germyl radicals having from 1-20 carbon, silicon, or germanium atoms,
• substituted hydrocarbyl, silyl or germyl radicals having from 1-20 carbon, silicon, or germanium atoms, in which one or more hydrogen atoms is replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical, an aryloxy radical or any other radical containing a Lewis acidic or basic functionality,
• C1-C20 hydrocarbyl-substituted Ge-, Sn-, or Pb-metalloid radicals,
• halogen radicals,
• amido radicals,
• phosphido radicals,
• alkoxy radicals, and
• alkylborido radicals;
• and optionally, at least two R1 groups are joined together to form, along with the carbon atoms to which they are attached, a C4-C20 ring structure, which is saturated or partially saturated, and substituted or unsubstituted, the optional ring-structure substitution being selected from one or more R1 groups as defined under (ii) above;
• (iii) X is selected from C, Si, Ge, Sn or Pb;
• (iv) m=1,
• (v) Y is selected from hydrocarbyl radicals, hydrosilyl radicals, and hydrogermyl radicals;
• and
• (vi) R2 is selected from unsubstituted C1-C20 hydrocarbyl, C1-C20 hydrocarbyl substituted with at least one Si, or C1-C20 hydrocarbyl substituted with at least one Ge;
• (vii) Q1 and Q2 are non-cyclopentadienyl radicals in which,
• independently, each Q is selected from halide, hydride, unsubstituted C1-C20 hydrocarbyl, C1-C20 hydrocarbyl substituted with at least one R1 group as defined under (ii) above, alkoxide, aryloxide, amide, halide, or phosphide;
• or
• together, Q1 and Q2 may form an alkylidene, cyclometallated hydrocarbyl, or any other divalent anionic chelating ligand.

A process for the preparation of ethylene copolymers with a density below 0.915 comprising contacting under solution polymerization conditions,

• ethylene,
• one or more α-olefin(s),
• optionally one or more diene(s), and
• a catalyst composition prepared from
• (a) alumoxane, and
• (b) at least one bis(cyclopentadienyl) zirconium compound having the following structure:
• where
• (i) Cp1 is an unsubstituted cyclopentadienyl ring,
• (ii) the substituted fluorenyl ring has at least two, non-hydrogen radical substituents, R1, independently selected from:
• hydrogen radical,
• unsubstituted hydrocarbyl, silyl or germyl radicals having from 1-20 carbon, silicon or germanium atoms,
• substituted hydrocarbyl, silyl or germyl radicals having from 1-20 carbon, silicon or germanium atoms, in which one or more hydrogen atoms is replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical, an aryloxy radical or any other radical containing a Lewis acidic or basic functionality,
• C1-C20 hydrocarbyl-substituted Ge-, Sn-, or Pb-metalloid radicals,
• halogen radicals,
• amido radicals,
• phosphido radicals,
• alkoxy radicals, and
• alkylborido radicals;
• (iii) and optionally, at least R1 groups are joined together to form, along with the carbon atoms to which they are attached, a C4-C20 ring structure, which is saturated or partially saturated, and substituted or unsubstituted, the ring structure substitution being selected from one or more R1 groups as defined under (ii) above;
• (iii) X is selected from C, Si, Ge, Sn and Pb;
• (iv) m=1,
• (v) Y is selected from hydrocarbyl radicals, hydrosilyl radicals, and hydrogermyl radicals;
• and
• (vi) R2 is selected from C1-C20 hydrocarbyl, C1-C20 hydrocarbyl substituted with at least one Si, and C1-C20 hydrocarbyl substituted with at least one Ge;
• (vii) Q1 and Q2 are non-cyclopentadienyl radicals in which
• independently, each Q is selected from halide, hydride, unsubstituted C1-C20 hydrocarbyl, C1-C20 hydrocarbyl substituted with at least one R1 group as defined under (ii) above, alkoxide, aryloxide, amide, halide or phosphide;
• or
• together, Q1 and Q2 may form an alkylidene, cyclometallated hydrocarbyl or any other divalent anionic chelating ligand.