EP1661900A1

Olefin polymerization cocatalysts derived from group-15 cationic compounds and processes using them

Abstract

Fluorinated amine compounds, R'iArF-ER2, where ArF is a fluo-roaryl substituent, E is nitrogen or phosphorous, each R is independently a C1-C20 hydrocarbyl substituent, or the two R's may be connected to form an unsubstituted or substituted C2-C20 cycloaliphatic substituent, R' is a C1-C20 hydrocarbyl or halogenated hydrocarbyl, and i is 0, 1 or 2 are disclosed. These compounds may be protonated and complexed with suitable substantially noncoordinating anions to prepare polymerization catalyst components. When these catalyst components are combined with organometallic catalyst precursors, the catalyst precursor is activated to a catalyst. This catalyst is combined with monomer under olefin polymerization conditions to prepare polymer. High number-average molecular weight polymers at high productivity rates were observed from using metallocene catalysts activated with [N-pentafluorophenyl pyrrolidinium] [tetrakis(pentafluorophenyl) borate].

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Projected expiry passed 11 December 2020, 5.8 years ago.

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22 claims: 17 independent, 5 dependent

  1. 1
    A compound with the formula:[R'iArF-ER2-H]+[A]-, where (a) ArF is a fluoroaryl group;(b) E is nitrogen or phosphorous;(c) each R is independently a C1-C20 linear or branched, hydrocarbyl or hydrocarbylsilyl group, or two Rs may connect to form an unsubstituted or substituted, halogenated or non-halogenated, C2-C20 cycloaliphatic, C2-C10 hydrocarbyl, or C2-C10 hydrocarbylsilyl;(d) R' is a C1-C20 hydrocarbyl or halogenated hydrocarbyl;(e) i is 0, 1, or 2;and(f) [A]- is a 4-coordinate Group 13 anion.
  2. 3
    The compound of any of the preceding claims wherein ArF is a fluorinated or perfluorinated aryl group and is one of phenyl, biphenyl, substituted phenyl, substituted biphenyl, terphenyl, or substituted terphenyl.
  3. 4
    The compound of any of the preceding claims wherein -R2- is a substituted or unsubstituted, halogenated or non-halogenated, C2-C20 cycloaliphatic group.
  4. 5
    The compound of any of the preceding claims wherein -E is nitrogen.
  5. 6
    The compound of any of the preceding claims wherein i is 1, ArF is fluorophenyl and R'- is at the para-position of ArF.
  6. 7
    A composition of matter that is the reaction product of (a) a fluoroaryl-ligand-substituted amine or phosphine with the formula:R'iArF-ER2, where (i) ArF is a fluoroaryl group;(ii) E is nitrogen or phosphorous;(iii) each R is independently a C1-C20 linear or branched, hydrocarbyl or hydrocarbylsilyl group, or two Rs may connect to form an unsubstituted or substituted, halogenated or non-halogenated, C2-C20 cycloaliphatic, C2-C10 hydrocarbyl, or C2-C10 hydrocarbylsilyl;(iv) R' is a C1-C20 hydrocarbyl or halogenated hydrocarbyl;(v) i is 0, 1, or 2;and(b) a precursor acid of a 4-coordinate Group 13 anion.
  7. 9
    The composition of any of claims 7 or 8 wherein ArF is a fluorinated or perfluorinated aryl group and is one of phenyl, substituted phenyl, biphenyl, and substituted biphenyl, terphenyl, or substituted terphenyl.
  8. 10
    The composition of any of claims 7 to 9 wherein -R2- is a substituted or unsubstituted, halogenated or non-halogenated, C2-C20 cycloaliphatic group.
  9. 11
    The composition of any of claims 7 to 10 wherein E is nitrogen.
  10. 12
    The composition of any of claims 7 to 11 wherein i is 1, ArF is fluoro phenyl and R' is in the para-position of ArF.
  11. 13
    A compound with the formula:[ArF-NR2-H] + [A] -, where (a) ArF is a fluoroaryl group;(b) each R is independently a C1-C20 hydrocarbyl or hydrocarbylsilyl group, or the two Rs may connect to form an unsubstituted or substituted C2-C20 cycloaliphatic group;and(c) [A]- is a 4-coordinate Group 13 anion.
  12. 15
    The compound of any of claims 13 or 14 wherein ArF is a fluorinated or perfluorinated aryl group and is one of phenyl, substituted phenyl, biphenyl, substituted biphenyl, terphenyl, or substituted terphenyl.
  13. 16
    The compound of any of claims 13 or 15 wherein ArF-NR2 is one of:N-pentafluorophenylpyrrolidine, N-paranonafluorobiphenyl-pyrolidine, N-tridecafluoroterphenylpyrolidine, N-penta-fluorophenylpyrrole, N-paranonafluorobiphenylpyrrole, N-tridecafluoroterphenylpyrrole, N-pentafluorophenylpiperidine, N-tridecafluoroterphenylpiperidine, N-pentafluorophenylindoline, N-paranonafluorobiphenylindoline, N-tridecafluoroterphenylindoline, N-pentafluorophenylindole, N-paranonafluorobiphenylindole, N-tridecafluoroterphenylindole, N-pentafluorophenylazetidine, N-paranonafluorobiphenylazetidine, N-tridecafluoroterphenylazetidine, N-pentafluorophenyaziridine, N-paranonafluorobiphenylaziridine, and N-tridecafluoroterphenylaziridine.
  14. 17
    The compound of any of claims 13 or 16 wherein ArF-NR2 is N-pentafluorophenylpyrrolidine.
  15. 18
    A process for the polymerization of olefins wherein a compound according to any of claims 1 to 6 is combined with a transition metal organometallic catalyst precursor compound to form an active olefin polymerization catalyst, and thereafter the catalyst is exposed to a monomer that has accessible olefinic, vinyic or acetylenic unsaturation.
  16. 19
    A process for the polymerization of olefins wherein a compound according to any of claims 13 to 17 is combined with a transition metal organometallic catalyst precursor compound to form an active olefin polymerization catalyst, and thereafter the catalyst is exposed to a monomer that has accessible olefinic, vinyic or acetylenic unsaturation.
  17. 22
    The process of any of claims 18 to 21 wherein the monomer is an olefin having from 2 to 20 carbon atoms.