High temperature polymerization process using ionic catalysts to produce polyolefins

Claim 2

A process for polymerizing one or more monomers from the group consisting of olefins, diolefins and acetylenically unsaturated monomers, comprising contacting at a temperature up to about 300 ° C. and a pressure from above about 500 bar to about 3445 bar in a suitable solvent or diluent, said monomers with an active polymerization catalyst comprising a cation of a mono- or bis(cyclopentadienyl) derivative of a group IV-B metal, and a compatible non-coordinating anion comprising boron or a plurality of boron atoms, said anion being sufficiently labile to permit displacement by said monomers.

Claim 3

The process of claim 1, wherein the catalyst system comprises one 20 or more of: ##STR5## wherein: (A-Cp) is either (Cp) (Cp*) or Cp-A'-Cp*; Cp and Cp* are the same or different cyclopentadienyl ring substituted with from zero to five substituent groups S, each substituent group S being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnictogen, substituted chalcogen or halogen radical, or Cp and Cp* are cyclopentadienyl rings in which two adjacent S groups are joined forming a C 4 to C 20 ring to form a saturated or unsaturated polycyclic cyclopentadienyl ligand; A' is a bridging group which restricts rotation of the Cp and Cp* tings or (C 5 H 5-y-x S x ) and (JS' z-1-y ) groups; (C 5 H 5-y-x S x ) is a cyclopentadienyl ring substituted with from zero to five S radicals: x is from 5 to 0 denoting the degree of substitution; M is titanium, zirconium or hafnium; X 1 is hydride radical, hydrocarbyl radical, substituted-hydrocarbyl radical, hydrocarbyl-substituted organometalloid radical or halocarbyl-substituted organometalloid radical which radical may optionally be covalently bonded to both or either M and L' or all or any M, S or S'; (JS' z-1-y ) is a heteroatom ligand in which J is an element from Group 15 of the Periodic Table of Elements with a coordination number of 3 or an element from Group 16 with a coordination number of 2; S' is a radical group which is a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organometalloid, or halocarbyl-substituted organometalloid; and z is the coordination number of the element J; y is 0 or 1; L' is an olefin, diolefin, aryne ligand, or an other neutral Lewis base or a second transition metal compound of the same type such that the two metal centers M and M* are bridged by X 1 and X' 1 , wherein M* has the same meaning as M and X' 1 has the same meaning as X 1 where such dimeric compounds which are precursors to the cationic transition metal species of the catalyst are represented by the formula: ##STR6## wherein: w is an integer from 0 to 3; B' is a chemically stable, non-nucleophilic anionic complex having a molecular diameter about or greater than 4 angstroms; and d is an integer representing the charge of B'.

Claim 4

The process of claim 1, wherein said solvent or diluent consists essentially of one or more polymerizable olefin(s).

Claim 5

The process of claim 1, wherein said α-olefin comprises ethylene.

Claim 6

The process of claim 1, wherein ethylene is polymerized in combination with another olefin selected from the group consisting of C 3-18 olefins, C 4-18 dienes, C 4-18 cyclic olefins or diolefins, C 4-18 aromatic containing olefins.

Claim 7

The process of claim 2, wherein [B'] d- is represented by the formula: [(M').sup.m+ Q.sub.1 Q.sub.2 . . . Q.sub.n ].sup.d- wherein: M' is a metal or metalloid; Q 1 to Q n are, independently, hydride radicals, bridged or unbridged, dialkylamido radicals, alkoxide and aryloxide radicals, hydrocarbyl and substituted-hydrocarbyl radicals, halocarbyl and substituted-halocarbyl radicals and hydrocarbyl and halocarbyl-substituted organometalloid radicals and any one, but not more than one, of Q 1 to Q n may be halide radicals; m is an integer representing the formal valence charge of M'; and n is the total number of ligands Q.

Claim 8

The process of claim 6, wherein [B'] d- is represented by the formula: [BAr.sub.1 Ar.sub.2 X.sub.3 X.sub.4 ]- wherein: B is boron in a valence state of 3; Ar 1 and Ar 2 are the same or different aromatic or substituted-aromatic hydrocarbon radicals containing from about 6 to about 20 carbon atoms and may be linked to each other through a stable bridging group; and X 3 and X 4 are, independently, hydride radicals, hydrocarbyl and substituted-hydrocarbyl radicals, halocarbyl and substituted-halocarbyl radicals, hydrocarbyl and halocarbyl-substituted organometalloid radicals, disubstituted pnictogen radicals, substituted chalcogen radicals and halide radicals, with the proviso that X 3 and X 4 will not both be halide.

Claim 9

The process of claim 7, wherein [B'] d- is reprersented by the formula: [B(C.sub.6 F.sub.5).sub.3 Q]- wherein: F is fluorine, C is carbon, B is boron and Q is a hydride radical, bridged or unbridged dialkylamido radical, alkoxide or aryloxide radical, hydrocarbyl or substituted-hydrocarbyl radical, halocarbyl or substituted-halocarbyl radical, hydrocarbyl or halocarbyl-substituted organometalloid radical, or halide radical.

Claim 10

The process of claim 8, wherein Q is a pentafluorophenyl radical.

Claim 11

The process of claim 9, wherein Q is a polymeric hydrocarbyl radical.

Claim 12

The process of claim 2, wherein [B'] d- is tetrapentafluorophenyl boron.

Claim 13

The process of claim 2, wherein [B'] d- is represented by: [(CX).sub.a (BX').sub.m X".sub.b ].sup.c- or [[[(CX.sub.6).sub.a '(BX.sub.7).sub.m' (X.sub.8)].sup.c'- ].sub.2 M".sup.n'+ ].sup.d' wherein: C is carbon; B is boron; X, X', X", X 6 , X 7 and X 8 are, independently, hydride radicals, halide radicals, hydrocarbyl radicals, substituted-hydrocarbyl radicals, halocarbyl radicals, substituted-halocarbyl radicals, or hydrocarbyl or halocarbyl-substituted organometalloid radicals; M" is a transition metal; a and b are integers ≧0; c is an integer ≧1; a+b+c=an even integer from 2 to about 8; and m is an integer ranging from 5 to about 22; a' and b' are the same or a different integer; c' is an integer ≧2; a'+b'+c'=an even-numbered integer from 4 to about 8; m' is an integer from 6 to about 12; n' is an integer such that 2c'=n'=d'; and d' is an integer ≧1.

Claim 14

The process of claim 1, wherein the said solvent or diluent is maintained at a temperature of about 180° C. to about 280° C.

Claim 15

The process of claim 1 wherein a molar ratio of cation to anion is in the range of 10:1 to about 1:1.

Claim 16

The process of claim 14 wherein the ratio is in the range of about 1 to about 1:1.

Claim 17

The process of claim 1 wherein the catalyst system is formed in-situ with the solvent or diluent.

Claim 18

The process according to claim 1 or 2 wherein said cyclopentadienyl derivative of a group IV-B metal comprises two cyclopentadienyl rings bound to the metal.

Claim 19

The process according to claim 1 or 2 wherein said cyclopentadienyl derivative of a group IV-B metal comprises a single cyclopentadienyl ring bound to the metal.