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US 10,647,798 B2Granted
Spray-dried olefin polymerization catalyst compositions and polymerization processes for using the same
AssigneeExxonMobil Chemical Patents Inc.
InventorsMatthew W. Holtcamp, Quanchang Li, David C. Calabro, Gerardo J. Majano Sanchez, Machteld M. Mertens, Charles J. Harlan
Life of this patent
Estimating the term…
Abstract
Disclosed herein are spray-dried catalyst compositions including one or more olefin polymerization catalysts and at least one support of an organosilica material, optionally, with at least one activator. The spray-dried catalyst compositions may be used in polymerization processes for the production of polyolefin polymers.
Claims24
A spray-dried catalyst composition comprising the product of:
- a first olefin polymerization catalyst;
- a second olefin polymerization catalyst;
- at least one catalyst support comprising an organosilica material that is a polymer of at least one monomer of the Formula [Z1OZ2SiCH2]3 (I), wherein Z1 is a hydrogen atom, a C1-C4 alkyl group or a bond to a silicon atom of another monomer and Z2 is a hydroxyl group, a C1-C4 alkoxy group, a C1-C6 alkyl group, or an oxygen atom bonded to a silicon atom of another monomer;
- and
- optionally, at least one activator, wherein:
- the first olefin polymerization catalyst comprises one or more metallocene catalysts represented by Formula (VII):
- TyCpmM6GnX5 q (VII),
- wherein each Cp is, independently, a cyclopentadienyl group which may be substituted or unsubstituted, M6 is a Group 4 transition metal, G is a heteroatom group represented by the Formula JR*z, wherein J is N, P, O or S, R* is a linear branched or cyclic hydrocarbyl group having from one to twenty carbon atoms, and z is 1 or 2, T is a bridging group, y is 0 or 1, X5 is a leaving group, m is 1 or 2, n is 0, 1, 2 or 3, q is 0, 1, 2 or 3, and the sum of m+n+q is equal to the oxidation state of the transition metal, and
- the second olefin polymerization catalyst comprises:
- (A) a compound represented by the Formula (VIII):
- wherein:
- M* is a Group 4 metal;
- the E′ groups are independently selected from carbon, silicon, or germanium;
- each X′ is an anionic leaving group;
- L* is a neutral Lewis base,
- R′1 and R′13 are independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups;
- R′2 and R′12 are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and phosphino;
- n′ is 1 or 2;
- m′ is 0, 1, or 2;
- and
- two X′ groups may be joined together to form a dianionic group;
- two L* groups may be joined together to form a bidentate Lewis base;
- an X′ group may be joined to an L* to form a monoanionic bidentate group;
- R′7 and R′8 may be joined to form a ring;
- and
- R′10 and R′11 may be joined to form a ring;
- (B) a compound represented by the Formula (IX):
- wherein:
- M is a Group 3-12 transition metal or a Group 13 or 14 main group metal;
- each X is independently an anionic leaving group;
- n is the formal oxidation state of M;
- m is the formal charge of the ligand comprising Y, Z, and L;
- Y is a Group 15 element;
- Z is a Group 15 element;
- R1 and R2 are independently a C1 to C20 hydrocarbon group, a heteroatom-containing group having up to twenty carbon atoms, silicon, germanium, tin, lead, phosphorus, or a halogen, wherein R1 and R2 may also be interconnected to each other;
- R3 is absent or a hydrocarbon group, hydrogen, a halogen, or a heteroatom-containing group;
- R4 and R5 are independently an aryl group, a substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic aralkyl group, a substituted cyclic aralkyl group, or a multiple ring system;
- and
- R6 and R7 are independently absent, or hydrogen, a halogen, a heteroatom, or a hydrocarbyl group;
- or
- (C) a compound represented by the Formula (X):
- wherein:
- M is a Group 7-9 transition metal;
- X is an atom or group covalently or ionically bonded to the transition metal M;
- n is 1, 2, 3, 4 or 5;
- and
- R1 to R7 are independently selected from the group consisting of hydrogen, halogens, hydrocarbyls, and substituted hydrocarbyls, provided that when any two or more of R1 to R7 are hydrocarbyl or substituted hydrocarbyl, two or more can be linked to form one or more cyclic substituents;
- and combinations thereof.
45 more elements
A spray-dried catalyst composition comprising the product of:
- a first olefin polymerization catalyst;
- a second olefin polymerization catalyst;
- at least one catalyst support comprising an organosilica material that is a polymer of at least one monomer of the Formula [Z1OZ2SiCH2]3 (I), wherein Z1 is a hydrogen atom, a C1-C4 alkyl group or a bond to a silicon atom of another monomer and Z2 is a hydroxyl group, a C1-C4 alkoxy group, a C1-C6 alkyl group, or an oxygen atom bonded to a silicon atom of another monomer;
- and
- optionally, at least one activator, wherein:
- the first olefin polymerization catalyst comprises one or more metallocene catalysts represented by Formula (VII):
- TyCpmM6GnX5q (VII),
- wherein each Cp is, independently, a cyclopentadienyl group which may be substituted or unsubstituted, M6 is a Group 4 transition metal, G is a heteroatom group represented by the Formula JR*z, wherein J is N, P, O or S, R* is a linear branched or cyclic hydrocarbyl group having from one to twenty carbon atoms, and z is 1 or 2, T is a bridging group, y is 0 or 1, X5 is a leaving group, m is 1 or 2, n is 0, 1, 2 or 3, g is 0, 1, 2 or 3, and the sum of m+n+g is equal to the oxidation state of the transition metal, and
- the second olefin polymerization catalyst comprises:
- a compound represented by the Formula (XI):
- wherein:
- M is selected from the group consisting of Ti, Zr, and Hf;
- R1 to R9 are independently selected from the group consisting of hydride, hydrocarbyl, lower hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, alkyl, lower alkyl, substituted alkyl, heteroalkyl, alkenyl, lower alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, lower alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, lower alkoxy, aryloxy, hydroxyl, alkylthio, lower alkyl thio, arylthio, thioxy, aryl, substituted aryl, heteroaryl, aralkyl, aralkylene, alkaryl, alkarylene, halide, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocycle, heteroaryl, heteroatom-containing group, silyl, boryl, phosphino, phosphine, amino, and amine;
- and X is at least one leaving group.
11 more elements
A spray-dried catalyst composition comprising the product of:
- a first olefin polymerization catalyst;
- a second olefin polymerization catalyst;
- at least one catalyst support comprising an organosilica material that is a polymer of at least one monomer of the Formula [Z1OZ2SiCH2]3 (I), wherein Z1 is a hydrogen atom, a C1-C4 alkyl group, or a bond to a silicon atom of another monomer and Z is a hydroxyl group, a C1-C4 alkoxy group, a C1-C6 alkyl group, or an oxygen atom bonded to a silicon atom of another monomer;
- and
- optionally, at least one activator, wherein:
- the first olefin polymerization catalyst comprises one or more metallocene catalysts represented by Formula (VII):
- TyCpmM6GnX5q (VII),
- wherein each Cp is, independently, a cyclopentadienyl group which may be substituted or unsubstituted, M6 is a Group 4 transition metal, G is a heteroatom group represented by the Formula JR*z, wherein J is N, P, O or S, R* is a linear branched or cyclic hydrocarbyl group having from one to twenty carbon atoms, and z is 1 or 2, T is a bridging group, y is 0 or 1, X5 is a leaving group, m is 1 or 2, n is 0, 1, 2 or 3, q is 0, 1, 2 or 3, and the sum of m+n+q is equal to the oxidation state of the transition metal, and
- the second olefin polymerization catalyst comprises:
- (A) a compound represented by the Formula (XII):
- wherein:
- each solid line represents a covalent bond and each dashed line represents a coordinative link;
- M is a Group 3-6 transition metal;
- N1 and N2 are nitrogen;
- O is oxygen;
- X1 and X2 are independently a univalent C1 to C20 hydrocarbyl radical, a functional group comprising elements from Groups 13-17, or X1 and X2 join together to form a C4 to C62 cyclic or polycyclic ring structure, provided however when M is trivalent X2 is not present;
- R1 to R6 and R12 to R17 are independently hydrogen, a C1 to C40 hydrocarbyl radical, a C1 to C40 substituted hydrocarbyl radical, two or more of R1 to R6 and R12 to R17 independently join together to form a C4 to C62 cyclic or polycyclic ring structure, or a combination thereof;
- R*1 and R*2 independently comprise a bulky functional group, an electron withdrawing group, or a combination thereof;
- and
- Y is a divalent C1 to C20 hydrocarbyl radical;
- (B) a compound represented by the Formula (XIII):
- wherein:
- M is a Group 4 transition metal;
- X1 and X2 are independently a univalent C1 to C20 hydrocarbyl radical, a C1 to C20 substituted hydrocarbyl radical, a heteroatom or a heteroatom-containing group, or X1 and X2 join together to form a C4 to C62 cyclic or polycyclic ring structure;
- R1 to R10 are independently a hydrogen, a C1 to C40 hydrocarbyl radical, a C1 to C40 substituted hydrocarbyl radical, a heteroatom or a heteroatom-containing group, or two or more of R1 to R10 may independently join together to form a C4 to C62 cyclic or polycyclic ring structure, or a combination thereof;
- Q is a neutral donor group;
- J is a C7 to C60 fused polycyclic group, which optionally comprises up to 20 atoms from Groups 15 and 16, wherein at least one ring is aromatic and wherein at least one ring, which may or may not be aromatic, has at least five members;
- G is as defined for J or may be hydrogen, a C1 to C60 hydrocarbyl radical, a C1 to C60 substituted hydrocarbyl radical, a heteroatom or a heteroatom-containing group, or may independently form a C4 to C60 cyclic or polycyclic ring structure with R6, R7, or R8 or a combination thereof, or
- (C) a compound represented by the Formula (XIV):
- wherein:
- M is selected from the group consisting of Ti, Zr, and Hf;
- at least one of R1 to R9 is substituted with a moiety having the following structure (XV):
- wherein structure (XV) is attached at any one of R1 to R9 at the R10 or R11 position;
- at least one of nitrogen N1 or N2 of Structure (XV) forms a dative bond with M;
- and R1 to R11 are independently selected from the group consisting of hydride, hydrocarbyl, lower hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, alkyl, lower alkyl, substituted alkyl, heteroalkyl, alkenyl, lower alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, lower alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, lower alkoxy, aryloxy, hydroxyl, alkylthio, lower alkyl thio, arylthio, thioxy, aryl, substituted aryl, heteroaryl, aralkyl, aralkylene, alkaryl, alkarylene, halide, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocycle, heteroaryl, heteroatom-containing group, silyl, boryl, phosphino, phosphine, amino, and amine;
- X is a leaving group;
- and combinations thereof.
34 more elements
Dependencies are inferred from the claim text.