Cationic catalysts and process for using said catalysts
AssigneeExxonMobil Chemical Patents Inc.
InventorsTimothy Daniel Shaffer, Anthony Jay Dias, Ira David Finkelstein, Myron Bernard Kurtzman
Life of this patent
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Abstract
A cationic catalyst composition comprising a reactive cation and a compatible non-coordinating anion is preferably used at a temperature of 20° C. or less to produce olefin polymers, particularly polymers and copolymers of isobutylene.
Claims37
A process for polymerization of cationically polymerizable olefins comprising contacting under polymerization conditions, in the presence of one or more solvents, one or more olefins with a catalyst comprising:
- a cation, and
- a compatible non-coordinating anion,
- provided that if said olefin is styrene, a different olefin is also present if said cation is a cyclopentadienyl titanium metal cation.
A process for the production of a blend of a polymer of one or more coordination polymerizable monomers and a polymer of one or more cationically polymerization monomers comprising contacting a cyclopentadienyl transition metal cation with a compatible non-coordinating anion under polymerization conditions in one or more solvents with a coordination polymerizable monomer and a cationically polymerizable monomer.
A process to produce a polymer of a first olefin comprising contacting said first olefin under cationic polymerization conditions at a temperature between about −50° C. and about 0° C. in the presence of one or more solvents, with a catalyst system comprising a cation and a non-coordinating anion.
A process in accordance with claim 26 wherein one or more other olefins are present during polymerization to form a copolymer of said first olefin and said one or more other olefins by coordination polymerization using the same catalyst system.
A catalyst system comprising:
- (a) substituted carbocations represented by the formula:
- 20
- wherein R1, R2 and R3 are hydrogen, alkyl, aryl, aralkyl groups or derivatives thereof provided that only one of R1, R2 and R3 is hydrogen when any of R1, R2 and R3 is hydrogen;
- and
- (b) a non-coordinating anion.
A catalyst system represented by the formulae:
- 21
- wherein each G is independently hydrogen or a hydrocarbyl group, and g is an integer greater than or equal to 1 representing a number of monomer units —(CH2—CG2)— incorporated into a polymer chain;
- and
- NCA− is a non-coordinating anion.
A catalyst system comprising:
- (a) substituted silylium represented by the formula:
- 22
- wherein R1, R2 and R3 are hydrogen, alkyl, aryl, aralkyl groups or derivatives thereof provided that only one of R1, R2 and R3 is hydrogen when any of R1, R2 and R3 is hydrogen;
- and
- (b) a non coordinating anion.
A catalyst system represented by the formulae:
- 23
- wherein each G is independently hydrogen or a hydrocarbyl group, and g is an integer greater than or equal to 1 representing a number of monomer units —(CH2—CG2)— incorporated into a polymer chain;
- and,
- NCA− is a non-coordinating anion.
A catalyst system comprising:
- (a) a proton source;
- and
- (b) a non-coordinating anion.
A catalyst system comprising:
- (a) cationic compositions of germanium, tin or lead represented by the formula:
- 24
- wherein R1, R2 and R3 are hydrogen, alkyl, aryl, aralkyl groups or derivatives and M* is Ge, Sn or Pb, provided that only one of R1, R2 and R3 is hydrogen when any of R1, R2 and R3 is hydrogen;
- and
- (b) a non coordinating anion.
A catalyst system represented by any of the formulae A, B, C, or D:
- 25
- wherein each G is independently hydrogen or an aromatic or aliphatic group, and g is an integer greater than or equal to 1 representing a number of monomer units —(CH2—CG2)— incorporated into a polymer chain, and further wherein:
- (A-Cp) is either (Cp)(Cp*) or Cp-A′-Cp*;
- Cp and Cp* are the same or different cyclopentadienyl rings 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 radicals, or Cp and Cp* are cyclopentadienyl rings in which any two adjacent S groups are joined formng a C4 to C20 ring system to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
- R is a substituent on one of the cyclopentadienyl radicals which is also bonded to the metal atom;
- A′ is a bridging group, which group may serve to restrict rotation of the Cp and Cp* rings or (C5H5-y-xSx) and JR′(z-1-y) groups;
- M is a Group 4, 5, or 6 transition metal;
- y is 0 or 1;
- (C5H5-y-xSx) is a cyclopentadienyl ring substituted with from zero to five S radicals;
- x is from 0 to 5 denoting the degree of substitution;
- JR′(z-1-y) is a heteroatom ligand in which J is a Group 15 element with a coordination number of three or a Group 16 element with a coordination number of 2, preferably nitrogen, phosphorus, oxygen or sulfur;
- R″ is a hydrocarbyl group, preferably an alkyl group;
- X and X1 are independently a hydride radical, hydrocarbyl radical, substituted hydrocarbyl radical, halocarbyl radical, substituted halocarbyl radical, and hydrocarbyl- and halocarbyl-substituted organometalloid radical, substituted pnictogen radical, or substituted chalcogen radicals, and
- NCA is a non-coordinating anion.
A catalyst system represented by any of the formulae E, A, G and H:
- 26
- wherein B′ is a polymer of one or more monomers selected form the group consisting of iso(C4 to C24)olefins, alpha-heteroatom olefins, alpha-alkyl-styrenes, and halostyrenes, and further wherein:
- (A-Cp) is either (Cp)(Cp*) or Cp-A′-Cp*;
- Cp and Cp* are the same or different cyclopentadienyl rings 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, disubstitated pnicogen, substituted chalcogen or halogen radicals, or Cp and Cp* are cyclopentadienyl rings in which any two adjacent S groups are joined forming a C4 to C20 ring system to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
- R is a substituent on one of the cyclopentadienyl radicals which is also bonded to the metal atom;
- A′ is a bridging group, which group may serve to restrict rotation of the Cp and Cp* rings or (C5H5-y-xSx) and JR′(z-1-y) groups;
- M is a Group 4, 5, or 6 transition metal;
- y is 0 or 1;
- (C5H5-y-xSx) is a cyclopentadienyl ring substituted with from zero to five S radicals;
- x is from 0 to 5 denoting the degree of substitution;
- JR′(z-1-y) is a heteroatom ligand in which J is a Group 15 element with a coordination number of three or a Group 16 element with a coordination number of 2, preferably nitrogen, phosphorus, oxygen or sulfur;
- R″ is a hydrocarbyl group, preferably an alkyl group;
- X and X1 are independently a hydride radical, hydrocarbyl radical, substituted hydrocarbyl radical, halocarbyl radical, substituted halocarbyl radical, and hydrocarbyl- and halocarbyl-substituted organometalloid radical, substituted pnicogen radical, or substituted chalcogen radicals;
- and
- NCA is a non-coordinating anions.
Dependencies are inferred from the claim text.