Solution phase polymerization process

Abstract

A solution phase polymerization process comprises feeding two single site polymerization catalysts, a bridged phosphinimine catalyst and an unbridged phosphinimine catalyst, to a polymerization reactor along with ethylene and optionally one or more than one alpha-olefin to make a polyethylene composition comprising a first polyethylene component and a second polyethylene component. The first and second polyethylene components are produced by the bridged phosphinimine catalyst and the unbridged phosphinimine catalyst respectively and depending on the polymerization conditions may have divergent molecular weights and short chain branching contents (where short chain branching occurs if one or more than one alpha-olefin is fed to the reactor along with ethylene).

Description

[0001] SOLUTION PHASE POLYMERIZATION PROCESS

[0002] TECHNICAL FIELD

[0003] A bridged phosphinimine catalyst, and an unbridged phosphinimine catalyst are fed to a polymerization reactor to produce a polyethylene composition by polymerizing ethylene optionally along with one or more than one alpha-olefin.

[0004] BACKGROUND ART

[0005] Solution polymerization processes are generally carried out at temperatures above the melting point of the ethylene homopolymer or copolymer product being made. In a typical solution polymerization process, catalyst components, process solvent, ethylene, an alpha-olefin such as 1 -octene and hydrogen are fed under pressure to one or more reactors.

[0006] For ethylene polymerization, or ethylene copolymerization, reactor temperatures can range from about 80°C to above about 300°C while pressures generally range from about 3 MPag to about 45 MPag. The ethylene homopolymer or copolymer produced remains dissolved in the solvent under reactor conditions. The residence time of the solvent in the reactor is relatively short, for example, from about 1 second to about 20 minutes. The solution polymerization process can be operated under a wide range of process conditions that allow the production of a wide variety of polyethylenes. Post reactor, the polymerization reaction is quenched to prevent further polymerization, by adding a catalyst deactivator, and optionally passivated, by adding an acid scavenger. Once deactivated (and optionally passivated), the polymer solution is passed to a polymer recovery operation (a devolatilization system) where the ethylene homopolymer or copolymer is separated from process solvent, unreacted residual ethylene and unreacted optional a-olefm(s).

[0007] SUMMARY OF INVENTION

[0008] Provided is a solution phase polymerization process to make a polyethylene composition, the process comprising: feeding ethylene, a process solvent, a bridged phosphinimine catalyst, an unbridged phosphinimine catalyst, one or more than one catalyst activator, optionally one or more than one a-olefin and optionally hydrogen to a polymerization reactor to produce the polyethylene composition, wherein the polyethylene composition comprises a first polyethylene component which is made by the bridged phosphinimine catalyst and a second polyethylene component which is made by the unbridged phosphinimine catalyst. In an embodiment, a solution phase polymerization reactor is operated at a temperature of from 80°C to 330°C.

[0009] In an embodiment, a solution phase polymerization reactor is operated at a pressure of from 3 MPag to 45 MPag.

[0010] In an embodiment, a solution phase polymerization reactor is a continuously stirred tank reactor.

[0011] In an embodiment, a bridged phosphinimine catalyst is represented by formula I: wherein

[0012] M is Ti, Zr or Hf;

[0013] R1and R2are each independently selected from the group consisting of hydrogen and Rx; or R1and R2together with the P atom to which they are attached form a 3-10 membered heterocyclic group which is unsubstituted or further substituted by one or more substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; each Rxis independently selected from the group consisting of a halogen atom; a Ci-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom, C1-20 alkyl group, C1-20 alkoxy group, C7-20 alkylaryl group, C7-20 arylalkyl group, C6-20 aryl group, C6-20 aryloxy group, C7-20 alkylaryloxy group, and / or C7-20 arylalkyloxy group; an amido group of the formula -NR’ 2; a silyl group of the formula -Si(Ra)3; a germanyl group of the formula -Ge(Ra)3; and a phosphinimine group of the formula -N=P(Rb)(Rc)(Rd); wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group; wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group and C6-20 aryl group; and Rb, Rc, Rd, are each independently a C1-20 alkyl group; each X1is an activatable ligand; Cy is a cyclopentadienyl-type ligand covalently bound to L and coordinated to M via T|-bonding; and

[0014] L is a bridging group containing a contiguous chain of 2 or 3 atoms connecting P with Cy.

[0015] In an embodiment, an unbridged phosphinimine catalyst is represented by formula

[0016] II:

[0017] (Cyu)Mu(N=PRp3)(X1)2 (XI) wherein

[0018] Muis Ti, Zr or Hf;

[0019] Cyuis selected from the group consisting of unsubstituted cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl, substituted indenyl, unsubstituted fluorenyl and substituted fluorenyl; and

[0020] Rpare each independently selected from the group consisting of a hydrogen atom; a halogen atom; a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom, C1-20 alkyl group, C1-20 alkoxy group, C7-20 alkylaryl group, C7-20 arylalkyl group, C6-20 aryl group, C6-20 aryloxy group, C7-20 alkylaryloxy group, and / or C7-20 arylalkyloxy group; an amido group of the formula -NR’2; a silyl group of the formula -Si(Ra)3; a germanyl group of the formula -Ge(Ra)3; and a phosphinimine group of the formula -N=P(Rb)(Rc)(Rd); wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group; wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group and C6-20 aryl group; and Rb, Rc, Rd, are each independently a C1-20 alkyl group; and each X1is an activatable ligand.

[0021] In an embodiment M is Ti.

[0022] In an embodiment Muis Ti.

[0023] BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 shows the gel permeation chromatographs with Fourier transform infra-red (GPC-FTIR) detection obtained for polyethylene compositions (Polymerization Runs 1-8) made according to the present disclosure. The comonomer content, shown as the number of short chain branches per 1000 carbons (y-axis), is given relative to the copolymer molecular weight (x-axis). The upwardly sloping lines (from left to right) are the short chain branching (in short chain branches per 1000 carbons atoms) determined by FTIR. As can be seen in the Figure 1, the number of short chain branches increases at higher molecular weights, and hence the comonomer incorporation is said to be “reversed” for the polyethylene compositions made in Polymerization Runs 1-8.

[0025] Figure 2 shows the gel permeation chromatographs with refractive index detection (GPC-RI) obtained for polyethylene compositions (Polymerization Runs 1-8) made according to the present disclosure.

[0026] Figure 3 shows the temperature rising elution fractionation (CTREF) analysis and profile of polyethylene compositions made according to the present disclosure (Polymerization Runs 1-8). Figure 4 shows the corresponding weight percent of polymer material eluting in a CTREF analysis at a temperature of below 82°C as plotted against the mol ratio of bridged phosphinimine catalyst to unbridged phosphinimine catalyst used in a polymerization reactor.

[0027] Figure 5 shows the gel permeation chromatographs with Fourier transform infra-red (GPC-FTIR) detection obtained for polyethylene compositions made during Polymerization Runs 9-13. The comonomer content, shown as the number of short chain branches per 1000 carbons (y-axis), is given relative to the copolymer molecular weight (x-axis). The relatively flat, or downward sloping lines (from left to right) are the short chain branching (in short chain branches per 1000 carbons atoms) determined by FTIR.

[0028] Figure 6 shows the gel permeation chromatographs with refractive index detection (GPC-RI) obtained for polyethylene compositions made during Polymerization Runs 9-13.

[0029] Figure 7 shows the temperature rising elution fractionation analysis and profile of polyethylene compositions made during Polymerization Runs 9-13.

[0030] DESCRIPTION OF EMBODIMENTS

[0031] As used herein, the term “monomer” refers to a small molecule that may chemically react and become chemically bonded with itself or other monomers to form a polymer.

[0032] As used herein, the term “a -olefin” or “alpha-olefin” is used to describe a monomer having a linear hydrocarbon chain containing from 3 to 20 carbon atoms having a double bond at one end of the chain; an equivalent term is “linear a-olefin”. As used herein, the term “polyethylene” or “ethylene polymer”, refers to macromolecules produced from ethylene monomers and optionally one or more additional monomers; regardless of the specific catalyst or specific process used to make the ethylene polymer. In the polyethylene art, the one or more additional monomers are called “comonomer(s)” and often include a- olefins. The term “homopolymer” refers to a polymer that contains only one type of monomer. An “ethylene homopolymer” is made using only ethylene as a polymerizable monomer. The term “copolymer” refers to a polymer that contains two or more types of monomer. An “ethylene copolymer” is made using ethylene and one or more other types of polymerizable monomer. Common polyethylenes include high density polyethylene (HDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), ultralow density polyethylene (ULDPE), plastomers and elastomers. The term polyethylene also includes polyethylene terpolymers which may include two or more comonomers in addition to ethylene. The term polyethylene also includes combinations of, or blends of, the polyethylenes described above.

[0033] As used herein, the terms “hydrocarbyl”, “hydrocarbyl radical” or “hydrocarbyl group” refers to linear, branched, cyclic, acyclic, aliphatic, olefinic (i.e., has double bond unsaturation), acetylenic (i.e., has triple bond unsaturation) and aryl (aromatic) groups comprising hydrogen and carbon that are deficient by at least one hydrogen atom. Hence a person skilled in the art will understand that “hydrocarbyl group” includes by way of providing non-limiting examples, alkyl groups, which may be primary, secondary (such as for example a cycloalkyl group), or tertiary alkyl groups; alkenyl groups; alkynyl groups; and aryl groups. The term “cyclic hydrocarbyl group” is a subset of the term “hydrocarbyl group” and specifically connotes hydrocarbyl groups that comprise at least one cyclic moiety and which may have one or more than one aromatic ring, and / or one or more than one non-aromatic ring present within them. The term “acyclic hydrocarbyl group” is a subset of the term “hydrocarbyl group” and specifically connotes hydrocarbyl groups that do not have cyclic moieties such as aromatic or non-aromatic ring structures present within them.

[0034] As used herein, the term “heteroatom” includes any atom other than carbon and hydrogen that can be bound to carbon. The term “heteroatom containing” or “heteroatom containing hydrocarbyl group” means that one or more than one non carbon atom, not including a hydrogen atom, is present in the hydrocarbyl group. Some non-limiting examples of non-carbon atoms (and non-hydrogen atoms) that may be present is a heteroatom containing hydrocarbyl group are N, O, S, P and Si as well as halides such as for example F and / or Br as well as metals such as Sn. Some non-limiting examples of heteroatom containing hydrocarbyl groups include for example aryloxy groups, alkoxy groups, alkylaryloxy groups, arylalkyloxy, silyl groups, and siloxy groups. Further nonlimiting examples of heteroatom containing hydrocarbyl groups generally include for example imines, amine moieties, oxide moieties, phosphine moieties, ethers, ketones, heterocyclics, oxazolines, thioethers, and the like. The term “cyclic heteroatom containing hydrocarbyl group” is a subset of the term “heteroatom containing hydrocarbyl group” and specifically connotes heteroatom containing hydrocarbyl groups that comprise at least one cyclic moiety and which may have one or more than one aromatic ring, and / or one or more than one non-aromatic ring present within them. The term “acyclic heteroatom containing hydrocarbyl group” is a subset of the term “heteroatom containing hydrocarbyl group” and specifically connotes heteroatom containing hydrocarbyl groups that do not have cyclic moieties such as aromatic or non-aromatic ring structures present within them.

[0035] In an embodiment of the disclosure, a heteroatom containing hydrocarbyl group is a hydrocarbyl group containing from 1 to 3 atoms selected from the group consisting of boron, aluminum, silicon, germanium, nitrogen, phosphorous, oxygen and sulfur.

[0036] In an embodiment of the disclosure, a cyclic heteroatom containing hydrocarbyl group is a cyclic hydrocarbyl group containing from 1 to 3 atoms selected from the group consisting of boron, aluminum, silicon, germanium, nitrogen, phosphorous, oxygen and sulfur.

[0037] The term “heterocyclic group” is a subset of the term “cyclic heteroatom containing hydrocarbyl group” and specifically refers to ring systems having a carbon backbone that further comprises at least one heteroatom selected from the group consisting of for example boron, aluminum, silicon, germanium, nitrogen, phosphorous, oxygen and sulfur within a ring structure.

[0038] As used herein, an “alkyl radical” or “alkyl group” includes linear, branched and cyclic paraffin groups that are deficient by one hydrogen group; non-limiting examples include methyl (-CTh) and ethyl (-CH2CH3) groups. The term “alkenyl radical” or “alkenyl group” refers to linear, branched and cyclic hydrocarbons containing at least one carboncarbon double bond that is deficient by one hydrogen group. The term “alkynyl radical” or “alkynyl group” refers to linear, branched and cyclic hydrocarbons containing at least one carbon-carbon triple bond that is deficient by one hydrogen group.

[0039] As used herein, the term “aryl radical” or “aryl group” includes phenyl, naphthyl, pyridyl and other groups whose molecules have an aromatic ring structure; non-limiting examples include naphthalene, phenanthrene and anthracene.

[0040] An “arylalkyl” is a subset of an “alkyl group” and is an alkyl group having an aryl group pendant there from; non-limiting examples include benzyl, phenethyl and tolylmethyl. An “alkylaryl” group is a subset of an “aryl group” and is an aryl group having one or more alkyl groups pendant there from; non-limiting examples include tolyl, xylyl, mesityl and cumyl.

[0041] An “alkoxy group” is an oxy group having an alkyl group pendant there from; and includes for example a methoxy group, an ethoxy group, an iso-propoxy group, and the like. An “arylalkyloxy group” is an oxy group having an arylalkyl group pendent there from (for clarity, the alkyl moiety is bonded to the oxy moiety and the aryl group is bonded to the alkyl moiety).

[0042] An “aryloxy” group is an oxy group having an aryl group pendant there from; and includes for example a phenoxy group and the like. An “alkylaryloxy group” is an oxy group having an alkylaryl group pendent there from (for clarity, the aryl moiety is bonded to the oxy moiety and the alkyl group is bonded to the aryl moiety).

[0043] In the present disclosure, a hydrocarbyl group or a heteroatom containing hydrocarbyl group (or subsets of these groups, such as alkyl groups, alkoxy groups, aryl groups, aryloxy groups, etc.) may be further specifically defined as being unsubstituted or substituted. As used herein the term “unsubstituted” means that hydrogen groups are bounded to the molecular group that is referred to by the term unsubstituted. The term “substituted” means that the group referred to by this term possesses one or more moieties that have replaced one or more hydrogen groups in any position within the group; nonlimiting examples of moieties include halogen groups (F, Cl, Br), an alkyl group, an alkylaryl group, an arylalkyl group, an alkoxy group, an aryl group, an aryloxy group, an amido group, a silyl group or a germanyl group, hydroxyl groups, carbonyl groups, carboxyl groups, amine groups, phosphine groups, phenyl groups, naphthyl groups, Ci to Cio alkyl groups, C2 to Cio alkenyl groups, and combinations thereof.

[0044] An oxy group is well known to persons skilled in the art and may be represented by the formula -OR where each R group is hydrogen or a hydrocarbyl group or a heteroatom containing hydrocarbyl group. The R’ group in an oxy group may be substituted or unsubstituted (when a hydrocarbyl group or a heteroatom containing hydrocarbyl group).

[0045] An amido group is well known to persons skilled in the art and may be represented by the formula -NR 2 where each R group is hydrogen or a hydrocarbyl group or a heteroatom containing hydrocarbyl group. Each of the R’ groups in an amido group may be substituted or unsubstituted (when a hydrocarbyl group or a heteroatom containing hydrocarbyl group).

[0046] A phosphide group is well known to persons skilled in the art and may be represented by the formula -PR 2 where each R group is hydrogen or a hydrocarbyl group or a heteroatom containing hydrocarbyl group. Each of the R’ groups in a phosphide group may be substituted or unsubstituted (when a hydrocarbyl group or a heteroatom containing hydrocarbyl group).

[0047] A thiolate group is well known to persons skilled in the art and may be represented by the formula -SR where the R group is hydrogen or a hydrocarbyl group or a heteroatom containing hydrocarbyl group. An R’ group in a thiolate group may be substituted or unsubstituted (when a hydrocarbyl group or a heteroatom containing hydrocarbyl group).

[0048] In embodiments of the disclosure, any hydrocarbyl group and / or any heteroatom containing hydrocarbyl group may be unsubstituted or substituted.

[0049] The present disclosure is directed to the use of a mixed polymerization catalyst system in a single polymerization reactor, although additional polymerization reactors and additional polymerization catalysts (known to persons skilled in the art but not specifically defined herein) may also be used. In an embodiment, the mixed polymerization catalyst system is a mixed single site catalyst system comprising a bridged phosphinimine catalyst and an unbridged phosphinimine catalyst.

[0050] In embodiment, a bridged phosphinimine catalyst and an unbridged phosphinimine catalyst are fed separately to a single polymerization reactor.

[0051] In embodiment, a bridged phosphinimine catalyst and an unbridged phosphinimine catalyst are combined upstream of, and fed as a mixture, to a single polymerization reactor. The Bridged Phosphinimine Catalyst

[0052] A bridged phosphinimine catalyst, is, in the present invention, a group 4 metal based (e.g. Ti, Zr, or Hf) single site olefin polymerization catalyst which has two activatable ligands, a cyclopentadienyl-type ligand and a phosphinimine ligand in which the cyclopentadienyl-type ligand and the phosphinimine ligand are connected by a bridging group.

[0053] The use of any bridged phosphinimine catalyst is contemplated for use in embodiments of the present disclosure and some non-limiting examples of bridged phosphinimine catalysts which may be useful in embodiments of the disclosure can be found in WO 2023 / 187552, which is incorporated herein by reference.

[0054] In an embodiment a bridged phosphinimine catalyst has the formula I: wherein

[0055] M is Ti, Zr or Hf;

[0056] R1and R2are each independently selected from the group consisting of hydrogen and Rx; or R1and R2together with the P atom to which they are attached form a 3-10 membered heterocyclic group which is unsubstituted or further substituted by one or more substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; each Rxis independently selected from the group consisting of a halogen atom; a Ci-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom, C1-20 alkyl group, C1-20 alkoxy group, C7-20 alkylaryl group, C7-20 arylalkyl group, C6-20 aryl group, C6-20 aryloxy group, C7-20 alkylaryloxy group, and / or C7-20 arylalkyloxy group; an amido group of the formula -NR’ 2; a silyl group of the formula -Si(Ra)3; a germanyl group of the formula -Ge(Ra)3; and a phosphinimine group of the formula -N=P(Rb)(Rc)(Rd); wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and Ce-2o aryl group; wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group and C6-20 aryl group; and Rb, Rc, Rd, are each independently a C1-20 alkyl group; each X1is an activatable ligand;

[0057] Cy is a cyclopentadienyl-type ligand covalently bound to L and coordinated to M via T|-bonding; and

[0058] L is a bridging group connecting P with Cy.

[0059] In embodiments of the disclosure, L is a bridging group containing a contiguous chain of 2 or 3 atoms connecting P with Cy. By the phrase “contiguous chain of 2 or 3 atoms” it is meant that the atoms being referred to are bonded together in sequence, and to P at one end, and to Cy at the other end. By way of example, a contiguous chain of 2 atoms bonded together in sequence, and to P at one end, and to Cy at the other end, includes P — atom 1 — atom 2 — Cy, with each of atom 1 and / or atom 2 optionally having additional atom(s) bonded to atom 1 and / or atom 2 (e.g., hydrogen, carbon, nitrogen, oxygen, etc.) but not having the additional atoms positioned between atom 1 and atom 2. By way of another example, a contiguous chain of 3 atoms bonded together in sequence, and to P at one end, and to Cy at the other end, includes P — atom 1 — atom 2 — atom 3 — Cy, with each of atom 1, atom 2, and / or atom 3 optionally having additional atom(s) bonded to atom 1, atom 2, and / or atom 3 (e.g., hydrogen, carbon, nitrogen, oxygen, etc.) but not having the additional atoms positioned between atom 1 and atom 2 and between atom 2 and atom 3. Additionally, when L is a bridging group containing a contiguous chain of 2 or 3 atoms connecting P with Cy, L may have more than one contiguous chain of atoms connecting P with Cy so long as L contains somewhere in its structure a contiguous chain of only 2 or only 3 atoms connecting P with Cy.

[0060] In some embodiments, R1and R2are each independently selected from the group consisting of a halogen atom; a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom, C1-20 alkyl group, C1-20 alkoxy group, C7-20 alkylaryl group, C7-20 arylalkyl group, C6-20 aryl group, C6-20 aryloxy group, C7-20 alkylaryloxy group, and / or C7-20 arylalkyloxy group; an amido group of the formula -NR’2; a silyl group of the formula -Si(Ra)3; a germanyl group of the formula -Ge(Ra)3; and a phosphinimine group of the formula -N=P(Rb)(Rc)(Rd); wherein each R’ is independently selected from the group consisting of hydrogen, C 1-20 alkyl group, and C6-20 aryl group; wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group and C6-20 aryl group; and Rb, Rc, Rd, are each independently a C1-20 alkyl group.

[0061] In some embodiments, R1and R2are each independently selected from the group consisting of a halogen atom; a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom, C1-20 alkyl group, C1-20 alkoxy group, C7-20 alkylaryl group, C7-20 arylalkyl group, C6-20 aryl group, C6-20 aryloxy group, C7-20 alkylaryloxy group, and / or C7-20 arylalkyloxy group.

[0062] In some embodiments, R1and R2are each independently a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom, C1-20 alkyl group, C1-20 alkoxy group, C7-20 alkylaryl group, C7-20 arylalkyl group, C6-20 aryl group, C6-20 aryloxy group, C7-20 alkylaryloxy group, and / or C7-20 arylalkyloxy group. In some embodiments, R1and R2are each independently an unsubstituted C1-30 hydrocarbyl group.

[0063] In some embodiments, R1and R2are each independently an unsubstituted C1-20 hydrocarbyl group.

[0064] In some embodiments, R1and R2are each independently an unsubstituted C1-12 hydrocarbyl group.

[0065] In some embodiments, R1and R2are each independently a C1-20 alkyl group.

[0066] In some embodiments, R1and R2are each independently a C1-12 alkyl group.

[0067] In some embodiments, R1and R2are each independently a C1-9 alkyl group.

[0068] In some embodiments, R1and R2are each independently a branched C3-8 alkyl group.

[0069] In some embodiments, R1and R2are each independently a C6-20 aryl group.

[0070] In some embodiments, R1and R2are the same.

[0071] In some embodiments, R1and R2are each independently selected from the group consisting of isopropyl, cyclohexyl and tert-butyl.

[0072] In some embodiments, R1and R2are each an isopropyl group.

[0073] In some embodiments, R1and R2are each a cyclohexyl group.

[0074] In some embodiments, R1and R2are each a tert-butyl group.

[0075] In some embodiments, each R is a C1-8 alkyl group.

[0076] In some embodiments, each R is a C6-20 aryl group.

[0077] In some embodiments, each R is a methyl group.

[0078] In some embodiments, each R is a phenyl group.

[0079] In some embodiments, each Rais a C1-8 alkyl group.

[0080] In some embodiments, each Rais a C6-20 aryl group.

[0081] In some embodiments, each Rais a methyl group.

[0082] In some embodiments, each Rais an ethyl group.

[0083] In some embodiments, each Rais a phenyl group.

[0084] In some embodiments, each of Rb, Rc, Rdis a C1-12 alkyl group.

[0085] In some embodiments, each of Rb, Rc, Rdis a C1-9 alkyl group.

[0086] In some embodiments, each of Rb, Rc, Rdis a C1-6 alkyl group.

[0087] In some embodiments, each of Rb, Rc, Rdis a branched C3-8 alkyl group.

[0088] In some embodiments, each of Rb, Rc, Rdis an isopropyl group.

[0089] In some embodiments, each of Rb, Rc, Rdis a cyclohexyl group.

[0090] In some embodiments, each of Rb, Rc, Rdis a tert-butyl group. In some embodiments, R1and R2together with the P atom to which they are attached together form a 3-10 membered heterocyclic group which is unsubstituted or further substituted by one or more substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group.

[0091] In some embodiments, R1and R2together with the P atom to which they are attached together form a 4-6 membered heterocyclic group which is unsubstituted or further substituted by one or more substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group.

[0092] In some embodiments, R1and R2together with the P atom to which they are attached together form a 5-6 membered heterocyclic group which is unsubstituted or further substituted by one or more substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group.

[0093] Each X1is independently an activatable ligand. Each X1may be the same or different. In some embodiments, each X1is the same.

[0094] The term “activatable ligand” refers to a ligand which may be activated by a catalyst activator and / or a cocatalyst, to facilitate olefin polymerization. An activatable ligand X1may be cleaved from the metal centre M via a protonolysis reaction or abstracted from the metal centre M by suitable acidic or electrophilic catalyst activator compounds (also known as “co-catalysf ’ compounds) respectively, examples of which are described below. The activatable ligand X1may also be transformed into another ligand which is cleaved or abstracted from the metal centre M (e.g., a halide may be converted to an alkyl group). Without wishing to be bound by any single theory, protonolysis or abstraction reactions generate an active “cationic” metal centre which can polymerize olefins.

[0095] In some embodiments each X1is independently selected from the group consisting of a hydrogen atom; a halogen atom; a C1-10 hydrocarbyl group; a C1-10 alkoxy group; a Ce-io aryl oxide group, each of which said hydrocarbyl, alkoxy, and aryl oxide groups may be unsubstituted or further substituted by a halogen atom, a C1-8 alkyl group, a C1-8 alkoxy group, a Ce-io aryl or aryloxy group; an amido group which is unsubstituted (i.e. -NH2) or substituted by up to two Ci-8 alkyl groups (i.e. -NR’ 2, where each R’ = C1-8 alkyl); and a phosphide group which is unsubstituted (i.e. -PH2) or substituted by up to two C1-8 alkyl groups (i.e. -PR’2, where each R’ = C1-8 alkyl).

[0096] In some embodiments each X1is independently selected from the group consisting of halogen, hydrogen, an amido group of the formula -NR€2, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxide group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; wherein each Reis independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group.

[0097] In some embodiments, two activatable X1ligands may also be joined to one another and form for example, a substituted or unsubstituted diene ligand (i.e., 1,3-diene); or a delocalized heteroatom -containing group such as an acetate group.

[0098] In embodiments of the disclosure, each X1is independently selected from the group consisting of a halide atom, a C1-4 alkyl group and a benzyl group.

[0099] In embodiments of the disclosure, each each X1is independently selected from the group consisting of a C1-6 alkyl group, a C7-10 arylalkyl group, and a halogen.

[0100] In some embodiments each X1is independently selected from unsubstituted C1-6 alkyl and a halogen.

[0101] In embodiments, each X1is a halogen atom (e.g., chloride) or a hydrocarbyl group (e.g., methyl group, benzyl group).

[0102] In embodiments, each X1is a benzyl group.

[0103] In embodiments, each X1is a -CH2C6F5 group (i.e., a pentafluorobenzyl group).

[0104] In embodiments, each X1is methyl.

[0105] In some embodiments, each X1is independently methyl or Cl.

[0106] In some embodiments, each X1is halogen.

[0107] In some embodiments, each X1is Cl.

[0108] In some embodiments, M is Ti.

[0109] In some embodiments, M is Hf.

[0110] In some embodiments, M is Zr.

[0111] As used in the present disclosure, “Cy” represents a “cyclopentadienyl-type ligand” which contains within its structure a cyclopentadienyl moiety, which refers to a 5 -member carbon ring and which can coordinate to a metal centre through delocalized 71-bonding, or in some cases through o-bonding. In some embodiments, “Cy” represents a “cyclopentadienyl-type ligand” which contains within its structure a cyclopentadienyl moiety, which refers to a 5 -member carbon ring having delocalized n-bonding within the ring (e.g., aromaticity) and which can coordinate to a metal centre.

[0112] In the present disclosure, a cyclopentadienyl-type ligand, Cy, is covalently bound to L and coordinated to M via p- (or eta-) bonding. The skilled person understands that p- bonding denotes hapticity of a ligand and refers to the coordination of the Cy ligand to the metal centre M, typically by p5-bonding, but that p3-bonding and p '-bonding is also possible in some cases and depending on the nature of the cyclopentadienyl-type ligand.

[0113] In some embodiments, a cyclopentadienyl-type ligand, Cy, is covalently bound to L and coordinated to M via p5-bonding or p3-bonding, or p '-bonding.

[0114] In some embodiments, a cyclopentadienyl-type ligand, Cy, is covalently bound to L and coordinated to M via p5-bonding or p3-bonding.

[0115] In some embodiments, a cyclopentadienyl-type ligand, Cy, is covalently bound to L and coordinated to M via p5-bonding or p '-bonding.

[0116] In some embodiments, a cyclopentadienyl-type ligand, Cy is covalently bound to L and coordinated to M via p5-bonding.

[0117] In some embodiments, a cyclopentadienyl-type ligand, Cy is covalently bound to L and coordinated to M via p3-bonding.

[0118] In some embodiments, a cyclopentadienyl-type ligand, Cy is covalently bound to L and coordinated to M via p1-bonding.

[0119] As used herein, the term “cyclopentadienyl-type ligand” is meant to include ligands which contain at least one five-carbon ring which is bonded to the metal via eta-5 (or in some cases eta-3, or in some cases eta-1) bonding. Thus, the term “cyclopentadienyl-type ligands” includes, for example, unsubstituted cyclopentadienyl, singly or multiply substituted cyclopentadienyl, unsubstituted indenyl, singly or multiply substituted indenyl, unsubstituted fluorenyl and singly or multiply substituted fluorenyl. Hydrogenated versions of indenyl and fluorenyl ligands are also contemplated for use in the current disclosure, so long as the five-carbon ring which bonds to the metal via eta-5 (or in some cases eta-3, or eta-1) bonding remains intact.

[0120] In embodiments of the disclosure, substituents for a cyclopentadienyl ligand, an indenyl ligand (or hydrogenated version thereof) and a fluorenyl ligand (or hydrogenated version thereof) may be selected from the group consisting of a C1-30 hydrocarbyl group, which hydrocarbyl group may be unsubstituted or further substituted by for example a halogen (such as would be the case for a pentafluorobenzyl group, -CH2C6F5), a C1-20 alkoxy group, a C6-20 aryl group, a C6-20 aryloxy group (each of which may be further substituted by for example a halogen); an amido group which is unsubstituted or substituted by up to two C1-8 alkyl groups; a phosphide group which is unsubstituted or substituted by up to two C1-8 alkyl groups; a silyl group of the formula -Si(Ra)3 wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group and C6-20 aryl group; and a germanyl group of the formula - Ge(Ra)s wherein Rais as defined directly above.

[0121] In some embodiments, Cy is selected from the group consisting of heteroatom substituted cyclopentadienyl-type ligands, and heteroatom containing cyclopentadienyl-type ligands.

[0122] In some embodiments, Cy is selected from the group consisting of substituted or unsubstituted indcno| l .2- / ? |indolyl and indeno[2, l - / ? |indolyl ligands.

[0123] In some embodiments, Cy is selected from the group consisting of unsubstituted or substituted cyclopentadienyl ligands; unsubstituted or substituted cyclopentenophenanthryl ligands and hydrogenated versions thereof; unsubstituted or substituted indenyl ligands and hydrogenated versions thereof; unsubstituted or substituted fluorenyl ligands and hydrogenated versions thereof; unsubstituted or substituted octahydrofluorenyl ligands; and unsubstituted or substituted azulenyl ligands.

[0124] In some embodiments, Cy is a cyclopentadienyl ligand which is unsubstituted or substituted by up to four substituents independently selected from the group consisting of: halogen; a Ci-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; an oxy group, -OR’; an amido group, -NR 2; a phosphide group, -PR 2; a thiolate group, -SR ; a silyl group of the formula -Si(Ra)3; and a germanyl group of the formula -Ge(Ra)3; wherein two adjacent substituents on the cyclopentadienyl ligand may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group of the formula -NR 2, a phosphide group of the formula -PR 2, a thiolate group of the formula -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group; and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group.

[0125] In some embodiments, Cy is an indenyl ligand which is unsubstituted or substituted by up to six substituents independently selected from the group consisting of halogen; a Ci-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; an oxy group, -OR’; an amido group, -NR 2; a phosphide group, -PR 2; a thiolate group, -SR ; a silyl group of the formula -Si(Ra)3; and a germanyl group of the formula -Ge(Ra)3; wherein two adjacent substituents on the indenyl ligand may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group of the formula -NR 2, a phosphide group of the formula -PR 2, a thiolate group of the formula -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group; and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group.

[0126] In some embodiments, Cy is an fluorenyl ligand which is unsubstituted or substituted by up to eight substituents independently selected from the group consisting of halogen; a Ci-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; an oxy group, -OR’; an amido group, -NR 2; a phosphide group, -PR 2; a thiolate group, -SR ; a silyl group of the formula -Si(Ra)3; and a germanyl group of the formula -Ge(Ra)3; wherein two adjacent substituents on the fluorenyl ligand may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group of the formula -NR 2, a phosphide group of the formula -PR 2, a thiolate group of the formula -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group; and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group.

[0127] A person skilled in the art understands that an indenyl group is a hydrocarbyl group derived from the compound indene: indene

[0128] A person skilled in the art understands that a fluorenyl group is a hydrocarbyl group derived from the compound fluorene: fluorene

[0129] Like cyclopentadienyl, an indenyl, or a fluorenyl group is, after deprotonation, able to coordinate to a metal centre by r|5-bonding (or in some cases, r|3-bonding, or in some cases, p'-bonding).

[0130] In some embodiments, Cy is an unsubstituted or substituted indenyl ligand.

[0131] In some embodiments, Cy is an unsubstituted indenyl ligand.

[0132] In some embodiments, Cy is a substituted indenyl ligand.

[0133] In some embodiments, Cy is an unsubstituted or substituted fluorenyl ligand. In some embodiments, Cy is an unsubstituted fluorenyl ligand.

[0134] In some embodiments, Cy is a substituted fluorenyl ligand.

[0135] In some embodiments, Cy is an unsubstituted indenyl ligand attached to the L group at the 1 -position or the 2-position, wherein the positions on the indenyl rings are numbered as follows:

[0136] In some embodiments, Cy is unsubstituted indenyl ligand attached to the L group at the 1 -position.

[0137] In some embodiments, Cy is unsubstituted indenyl ligand attached to the L group at the 2-position.

[0138] In some embodiments, Cy is of the formula: wherein ' / vww' indicates the point of attachment to L and each of RA, RB, Rc, RD, REand RFare independently selected from H, C1-12 hydrocarbyl group and C1-12 heteroatom- containing hydrocarbyl group. In some embodiments each of RA, RB, Rc, RD, REand RFare independently selected from H and unsubstituted C1-6 alkyl group. In some embodiments each of RA, RB, RC, RD, REand RFare H. In some embodiments, two adjacent groups of RB, Rc, RDand REare bonded to form a ring.

[0139] In some embodiments, Cy is of the formula: wherein ^rwvw' indicates the point of attachment to L and each of RA, RB, Rc, RD, REand RFare independently selected from H, C1-12 hydrocarbyl group and C1-12 heteroatomcontaining hydrocarbyl group. In some embodiments each of RA, RB, Rc, RD, REand RFare independently selected from H and unsubstituted C1-6 alkyl group. In some embodiments each of RA, RB, RC, RD, REand RFare H. In some embodiments, two adjacent groups of RB, Rc, RDand REare bonded to form a ring.

[0140] In some embodiments, L is a bridging group containing a contiguous chain of 3 atoms connecting P with Cy. In some embodiments, L is a bridging group containing a contiguous chain of 2 atoms connecting P with Cy. By the phrases “contiguous chain of 3 atoms” and “contiguous chain of 2 atoms”, it is meant that the atoms being referred to are bonded together in sequence, and to P at one end, and to Cy at the other end.

[0141] In some embodiments, L is a bridging group containing at least one cyclic hydrocarbyl group or at least one cyclic heteroatom containing hydrocarbyl group.

[0142] In some embodiments, L is a bridging group containing at least one cycloalkylene, heterocycloalkylene, arylene or heteroarylene group. The term “cycloalkylene” refers to a bivalent group containing a cycloaliphatic ring. The term “heterocycloalkylene” refers to a bivalent group containing a heterocycloaliphatic ring. The term “arylene” refers to a bivalent group containing an aromatic ring. The term “heteroarylene” refers to a bivalent group containing a heteroaromatic ring.

[0143] In some embodiments, L is a bridging group containing at least one arylene or heteroarylene group.

[0144] In some embodiments, L is a bridging group containing at least one cycloalkylene, or heterocycloalkylene group.

[0145] In some embodiments, L is a bridging group comprising up to 50 atoms selected from carbon atoms, hydrogen atoms and heteroatoms and containing at least one phenylene group. In some embodiments L is a bridging group containing at least one arylene group. In some embodiments L is a bridging group containing at least one phenylene group.

[0146] In some embodiments L is a bridging group comprising up to 50 atoms selected from carbon atoms, hydrogen atoms and heteroatoms and contains at least one arylene or heteroarylene group. In some embodiments L is a bridging group comprising up to 50 atoms selected from carbon atoms, hydrogen atoms and heteroatoms and contains at least one arylene group. In some embodiments L is a bridging group comprising up to 50 atoms selected from carbon atoms, hydrogen atoms and heteroatoms and contains at least one phenylene group. In some embodiments L is a bridging group comprising up to 50 atoms selected from carbon atoms and hydrogen atoms and contains at least one phenylene group.

[0147] The arylene or heteroarylene group within L may be directly or indirectly covalently bound to P. The arylene or heteroarylene group within L may be directly covalently bound to P (i.e., there may be a covalent bond from P to an atom of the ring of the arylene or heteroarylene group). Alternatively, the arylene or heteroarylene group within L may be indirectly covalently bound to P (i.e., there may be a further bivalent group between P and an atom of the ring of the arylene or heteroarylene group). The further bivalent group may be a hydrocarbylene group, for example an alkylene group or alkenylene group, or may be a bivalent group containing one or more heteroatoms.

[0148] The arylene or heteroarylene group within L may be directly or indirectly covalently bound to Cy. The arylene or heteroarylene group within L may be directly covalently bound to Cy (i.e., there may be a covalent bond from Cy to an atom of the ring of the arylene or heteroarylene group). Alternatively, the arylene or heteroarylene group within L may be indirectly covalently bound to Cy (i.e., there may be a further bivalent group between Cy and an atom of the ring of the arylene or heteroarylene group). The further bivalent group may be a hydrocarbylene group, for example an alkylene group or alkenylene group, or may be a bivalent group containing one or more heteroatoms.

[0149] In some embodiments, L is a bridging group containing a contiguous chain of atoms connecting P with Cy, wherein the adjacent carbon atoms of a phenylene group form part of the contiguous chain of atoms.

[0150] In some embodiments L is selected from: wherein ^wvw' indicates the point of attachment to P and (*) indicates the point of attachment to Cy; wherein each RGis independently selected from the group consisting of halogen; a Ci-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; an oxy group, -OR’; an amido group, -NR 2; a phosphide group, -PR 2; a thiolate group, -SR ; a silyl group of the formula -Si(Ra)3; and a germanyl group of the formula -Ge(Ra)3; wherein two adjacent RGgroups may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group of the formula -NR 2, a phosphide group of the formula -PR 2, a thiolate group of the formula -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein RKand RLare each independently selected from the group consisting of halogen; hydrogen; a Ci-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; wherein the groups of RKand RLmay optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group of the formula -NR 2, a phosphide group of the formula -PR 2, a thiolate group of the formula -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group; and each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group.

[0151] In embodiments each RGis independently selected from halogen and unsubstituted C1-12 alkyl. In some embodiments RGis absent (the phenylene group, or the naphthalene group is unsubstituted).

[0152] In embodiments RKand RLare each independently selected from hydrogen, unsubstituted C1-12 alkyl group, and unsubstituted or substituted C6-20 aryl group.

[0153] In embodiments RKand RLare each independently selected unsubstituted C1-12 alkyl group, and unsubstituted or substituted C6-20 aryl group.

[0154] In some embodiments RKand RLare each hydrogen.

[0155] In some embodiments L is of the formula: wherein RMand RNare each independently selected from the group consisting of halogen; hydrogen; a Ci-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; an oxy group, -OR’; an amido group, -NR 2; a phosphide group, -PR 2; a thiolate group, -SR ; a silyl group of the formula -Si(Ra)3; and a germanyl group of the formula -Ge(Ra)3; wherein two adjacent groups of RMand RNmay optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group of the formula -NR 2, a phosphide group of the formula -PR 2, a thiolate group of the formula -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group; and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group; wherein x rww' indicates the point of attachment to P and (*) indicates the point of attachment to Cy.

[0156] In some embodiments, RMand RNare each independently selected from the group consisting of halogen, hydrogen, a C1-30 alkyl group, a C1-30 alkoxy group, a C7-30 alkylaryl group, a C7-30 arylalkyl group, a Ce-30 aryl group, a Ce-3o.aryloxide group, a C7-30 alkylaryloxy group, and a C7-30 arylalkyloxy group.

[0157] In some embodiments, RMand RNare each independently selected from the group consisting of halogen, hydrogen, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxide group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group.

[0158] In some embodiments, the RMand RNgroups are bonded to form a cyclic hydrocarbyl group.

[0159] In some embodiments, the RMand RNgroups are bonded to form a phenylene group, the phenylene group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group, -NR 2, a phosphide group, -PR 2, a thiolate group, -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group; and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group and C6-20 aryl group. In some embodiments, the RMand RNgroups are bonded to form a phenylene group which is not further substituted.

[0160] In some embodiments L is of the formula: wherein R°, R0*, Rpand Rp* are each independently selected from the group consisting of halogen; hydrogen; a Ci-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; an oxy group, -OR’; an amido group, -NR 2; a phosphide group, -PR 2; a thiolate group, -SR ; a silyl group of the formula -Si(Ra)3; and a germanyl group of the formula -Ge(Ra)3; wherein two groups among R°, R0*, Rp, Rp* may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group of the formula -NR 2, a phosphide group of the formula -PR 2, a thiolate group of the formula -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group; and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group; and wherein n vvvv' indicates the point of attachment to P and (*) indicates the point of attachment to Cy.

[0161] In some embodiments, R°, R0*, Rpand Rp* are each independently selected from the group consisting of halogen, hydrogen, a C1-30 alkyl group, a C1-30 alkoxy group, a C7-30 alkylaryl group, a C7-30 arylalkyl group, a Ce-30 aryl group, a Ce-30 aryloxide group, a C7-30 alkylaryloxy group, and a C7-30 arylalkyloxy group.

[0162] In some embodiments, R°, R0*, Rpand Rp* are each independently selected from the group consisting of halogen, hydrogen, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxide group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group.

[0163] In some embodiments, one R° group and one Rpgroup are bonded to form a cyclic hydrocarbyl group.

[0164] In some embodiments, one R° group and one Rpgroup are bonded to form a cyclohexyl group.

[0165] In some embodiments L is of the formula: wherein RKand RLare each independently selected from hydrogen, unsubstituted C1-12 alkyl group, and unsubstituted or substituted C6-20 aryl group;

[0166] RMand RNare each independently selected from the group consisting of halogen; hydrogen; a Ci-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; an oxy group, -OR’; an amido group, -NR 2; a phosphide group, -PR 2; a thiolate group, -SR ; a silyl group of the formula -Si(Ra)3; and a germanyl group of the formula -Ge(Ra)3; wherein two adjacent groups of RMand RNmay optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group of the formula -NR 2, a phosphide group of the formula -PR 2, a thiolate group of the formula -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group; and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group; wherein ' / vvvv' indicates the point of attachment to P and (*) indicates the point of attachment to Cy.

[0167] In some embodiments, RMand RNare each independently selected from the group consisting of halogen, hydrogen, a C1-30 alkyl group, a C1-30 alkoxy group, a C7-30 alkylaryl group, a C7-30 arylalkyl group, a Ce-30 aryl group, a Ce-30 aryloxide group, a C7-30 alkylaryloxy group, and a C7-30 arylalkyloxy group. In some embodiments, RMand RNare each independently selected from the group consisting of halogen, hydrogen, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxide group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group.

[0168] In some embodiments, the RMand RNgroups are bonded to form a cyclic hydrocarbyl group.

[0169] In some embodiments, the RMand RNgroups are bonded to form a phenylene group, the phenylene group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group, , a phosphide group, -PR 2, a thiolate group, -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group; and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group and C6-20 aryl group.

[0170] In some embodiments, the RMand RNgroups are bonded to form a phenylene group which is not further substituted.

[0171] In some embodiments L is of the formula: wherein RKand RLare each independently selected from hydrogen, unsubstituted Ci-12 alkyl group, and unsubstituted or substituted C6-20 aryl group; wherein R°, R0*, Rpand Rp* are each independently selected from the group consisting of halogen; hydrogen; a Ci-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a Ce-20 aryl group, a Ce-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; an oxy group, -OR’; an amido group, -NR 2; a phosphide group, -PR 2; a thiolate group, -SR ; a silyl group of the formula -Si(Ra)3; and a germanyl group of the formula -Ge(Ra)3; wherein two groups among R°, R0*, Rp, Rp* may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group of the formula -NR 2, a phosphide group of the formula -PR 2, a thiolate group of the formula -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group; and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group; and wherein ' / vww' indicates the point of attachment to P and (*) indicates the point of attachment to Cy.

[0172] In some embodiments, R°, R0*, Rpand Rp* are each independently selected from the group consisting of halogen, hydrogen, a C1-30 alkyl group, a C1-30 alkoxy group, a C7-30 alkylaryl group, a C7-30 arylalkyl group, a Ce-30 aryl group, a Ce-30 aryloxide group, a C7-30 alkylaryloxy group, and a C7-30 arylalkyloxy group.

[0173] In some embodiments, R°, R0*, Rpand Rp* are each independently selected from the group consisting of halogen, hydrogen, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxide group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group.

[0174] In some embodiments, one R° group and one Rpgroup are bonded to form a cyclic hydrocarbyl group.

[0175] In some embodiments, one R° group and one Rpgroup are bonded to form a cyclohexyl group.

[0176] In some embodiments L is of the formula: wherein RKand RLare each independently selected from hydrogen, unsubstituted C1-12 alkyl group, and unsubstituted or substituted C6-20 aryl group; wherein R° and R°* are each independently selected from the group consisting of halogen; hydrogen; a Ci-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; an oxy group, -OR’; an amido group, -NR 2; a phosphide group, -PR 2; a thiolate group, -SR ; a silyl group of the formula -Si(Ra)3; and a germanyl group of the formula -Ge(Ra)3; wherein two groups among R° and R°* may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group of the formula -NR 2, a phosphide group of the formula -PR 2, a thiolate group of the formula -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group; and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group; and wherein oxrcn vv' indicates the point of attachment to P and (*) indicates the point of attachment to Cy.

[0177] In some embodiments, R° and R°* are each independently selected from the group consisting of halogen, hydrogen, a C1-30 alkyl group, a C1-30 alkoxy group, a C7-30 alkylaryl group, a C7-30 arylalkyl group, a Ce-30 aryl group, a Ce-30 aryloxide group, a C7-30 alkylaryloxy group, and a C7-30 arylalkyloxy group.

[0178] In some embodiments, R° and R°* are each independently selected from the group consisting of halogen, hydrogen, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxide group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group.

[0179] In some embodiments L is of the formula: wherein RM, RN, R°. and R°* are each independently selected from the group consisting of halogen; hydrogen; a Ci-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; an oxy group, -OR’; an amido group, -NR 2; a phosphide group, -PR 2; a thiolate group, -SR ; a silyl group of the formula -Si(Ra)3; and a germanyl group of the formula -Ge(Ra)3; wherein two adjacent groups of RMand RNmay optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group of the formula -NR 2, a phosphide group of the formula -PR 2, a thiolate group of the formula -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein two groups among R° and R°* may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group of the formula -NR 2, a phosphide group of the formula -PR 2, a thiolate group of the formula -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, Ci-20 alkyl group, and Ce-20 aryl group; and wherein each Rais independently selected from the group consisting of hydrogen, Ci-8 alkyl group, Ci-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group; and wherein indicates the point of attachment to P and (*) indicates the point of attachment to Cy.

[0180] In some embodiments, RMand RNare each independently selected from the group consisting of halogen, hydrogen, a C1-30 alkyl group, a C1-30 alkoxy group, a C7-30 alkylaryl group, a C7-30 arylalkyl group, a Ce-30 aryl group, a Ce-30 aryloxide group, a C7-30 alkylaryloxy group, and a C7-30 arylalkyloxy group.

[0181] In some embodiments, RMand RNare each independently selected from the group consisting of halogen, hydrogen, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxide group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group.

[0182] In some embodiments, the RMand RNgroups are bonded to form a cyclic hydrocarbyl group.

[0183] In some embodiments, the RMand RNgroups are bonded to form a phenylene group, the phenylene group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group, -NR 2, a phosphide group, -PR 2, a thiolate group, -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group; and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group and C6-20 aryl group.

[0184] In some embodiments, the RMand RNgroups are bonded to form a phenylene group which is not further substituted.

[0185] In some embodiments, R° and R°* are each independently selected from the group consisting of halogen, hydrogen, a C1-30 alkyl group, a C1-30 alkoxy group, a C7-30 alkylaryl group, a C7-30 arylalkyl group, a Ce-30 aryl group, a Ce-30 aryloxide group, a C7-30 alkylaryloxy group, and a C7-30 arylalkyloxy group.

[0186] In some embodiments, R° and R°* are each independently selected from the group consisting of halogen, hydrogen, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxide group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group.

[0187] In embodiments, a silyl group has the formula -Si(Ra)3, wherein the Ragroups are independently selected from a hydrogen atom, a C1-8 alkyl or alkoxy group, a Ce-io aryl group, and a Ce-io aryloxy group.

[0188] In embodiments, a silyl group has the formula -Si(Ra)3, wherein the Ragroups are independently selected from a C1-8 alkyl or alkoxy group, a Ce-io aryl group, and a Ce-io aryloxy group.

[0189] In some embodiments of the disclosure, an oxy group has the formula -OR , wherein the R group is selected from the group consisting of a hydrogen atom, a C1-10 alkyl group, and a Ce-io aryl group.

[0190] In some embodiments of the disclosure, an oxy group has the formula -OR , wherein the R group is selected from the group consisting of a C1-10 alkyl group, and a Ce-io aryl group.

[0191] In some embodiments of the disclosure, an amido group has the formula -NR 2, wherein the R groups are independently selected from the group consisting of a hydrogen atom, a C1-10 alkyl group, a Ce-io aryl group.

[0192] In some embodiments of the disclosure, an amido group has the formula -NR 2, wherein the R groups are independently selected from the group consisting of a C1-10 alkyl group, and a Ce-io aryl group.

[0193] In some embodiments of the disclosure, a phosphide group has the formula -PR 2, wherein the R groups are independently selected from the group consisting of a hydrogen atom, a C1-10 alkyl group, and a Ce-io aryl group.

[0194] In some embodiments of the disclosure, a phosphide group has the formula -PR 2, wherein the R groups are independently selected from the group consisting of a C1-10 alkyl group, and a Ce-io aryl group.

[0195] In some embodiments of the disclosure, a thiolate group has the formula -SR , wherein the R group is selected from the group consisting of a hydrogen atom, a C1-10 alkyl group, and a Ce-io aryl group.

[0196] In some embodiments of the disclosure, a thiolate group has the formula -SR , wherein the R group is selected from the group consisting of a C1-10 alkyl group, and a Ce-io aryl group.

[0197] In embodiments of the disclosure, the bridged phosphinimine catalyst of formula I, is bridged phosphinimine catalyst represented by formula IA:

[0198] wherein R1, R2, X1and Cy are as defined above for formula I.

[0199] In embodiments of the disclosure, the bridged phosphinimine catalyst, is a bridged phosphinimine catalyst by formula IB: wherein R1, R2, RK, RL, X1and Cy are as defined above for formula I.

[0200] In embodiments of the disclosure, the bridged phosphinimine catalyst of formula I, is a bridged phosphinimine catalyst represented by formula IC: wherein each of R1, R2and X1are as defined above for formula I.

[0201] In embodiments of the disclosure, the bridged phosphinimine catalyst of formula I, is a bridged phosphinimine catalyst represented by formula IC* : wherein each of R1, R2and X1are as defined above for formula I.

[0202] In embodiments of the disclosure, the bridged phosphinimine catalyst of formula I, is a bridged phosphinimine catalyst represented by formula II: wherein M, R1, R2, X1and L are as defined above for formula I; and wherein R3, R4, R5and R6are each independently selected from the group consisting of: halogen; hydrogen; a Ci-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; an oxy group, -OR’; an amido group, -NR 2; a phosphide group, -PR 2; a thiolate group, -SR ; a silyl group of the formula -Si(Ra)3; and a germanyl group of the formula -Ge(Ra)3; wherein two adjacent groups of R3, R4, R5and R6may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group of the formula -NR 2, a phosphide group of the formula -PR 2, a thiolate group of the formula -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group; and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group.

[0203] In some embodiments, R3, R4, R5and R6are each independently selected from the group consisting of halogen; hydrogen; a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; and a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; where two adjacent groups of R3, R4, R5and R6may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group, -NR 2, a phosphide group, -PR 2, a thiolate group, -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group.

[0204] In some embodiments, R3, R4, R5and R6are each independently selected from the group consisting of halogen; hydrogen; and a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7- 20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; where two adjacent groups of R3, R4, R5and R6may optionally be bonded to form a cyclic hydrocarbyl group, the cyclic hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-2 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group, -NR 2, a phosphide group, -PR 2, a thiolate group, -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group.

[0205] In some embodiments, R3, R4, R5and R6are each independently selected from the group consisting of halogen; hydrogen; and a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; where two adjacent groups of R3, R4, R5and R6may optionally be bonded to form a cyclic heteroatom containing hydrocarbyl group, the cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group, -NR 2, a phosphide group, -PR 2, a thiolate group, -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group.

[0206] In some embodiments, R3, R4, R5and R6are each independently selected from the group consisting of halogen, hydrogen, a C1-30 alkyl group, a C1-30 alkoxy group, a C7-30 alkylaryl group, a C7-30 arylalkyl group, a Ce-30 aryl group, a Ce-30 aryloxide group, a C7-30 alkylaryloxy group, and a C7-30 arylalkyloxy group.

[0207] In some embodiments, R3, R4, R5and R6are each independently selected from the group consisting of halogen, hydrogen, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxide group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group.

[0208] In some embodiments, R3, R4, R5and R6are each independently selected from the group consisting of halogen, hydrogen, and a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom.

[0209] In some embodiments, R3, R4, R5and R6are each independently selected from the group consisting of halogen, hydrogen, and a C1-30 heteroatom containing hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom.

[0210] In some embodiments, R3, R4, R5and R6are each independently selected from the group consisting of hydrogen and a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom.

[0211] In some embodiments, R3, R4, R5and R6are each independently selected from the group consisting of hydrogen and a C1-30 heteroatom containing hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom.

[0212] In some embodiments, R3, R4, R5and R6are each hydrogen.

[0213] In embodiments of the disclosure, the bridged phosphinimine catalyst of formula II, is a bridged phosphinimine catalyst represented by formula III: wherein M, R1, R2, R3, R4, R5, R6, and X1are as defined above for formulas I and II; and wherein R7, R8, R9and R10are each independently selected from the group consisting of halogen; hydrogen; a Ci-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; an oxy group, -OR’; an amido group, -NR 2; a phosphide group, -PR 2; a thiolate group, -SR ; a silyl group of the formula -Si(Ra)3; and a germanyl group of the formula -Ge(Ra)3; wherein two adjacent groups of R7, R8, R9and R10may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group of the formula -NR 2, a phosphide group of the formula -PR 2, a thiolate group of the formula -SR ,a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group; and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group.

[0214] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of halogen; hydrogen; a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; and a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; where two adjacent groups of R7, R8, R9and R10may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group, -NR 2, a phosphide group, -PR 2, a thiolate group, -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group.

[0215] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of halogen; hydrogen; and a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7- 20 alkylaryloxy group, and a C7-20 arylalkyloxy group; where two adjacent groups of R7, R8, R9and R10may optionally be bonded to form a cyclic hydrocarbyl group, the cyclic hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group, -NR 2, a phosphide group, -PR 2, a thiolate group, -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group.

[0216] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of halogen; hydrogen; and a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; where two adjacent groups of R7, R8, R9and R10may optionally be bonded to form a cyclic heteroatom containing hydrocarbyl group, the cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a Ce-2o aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, , an amido group, -NR 2, a phosphide group, -PR 2, a thiolate group, -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group.

[0217] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of halogen, hydrogen, a C1-30 alkyl group, a C1-30 alkoxy group, a C7-30 alkylaryl group, a C7-30 arylalkyl group, a Ce-so aryl group, a Ce-30 aryloxide group, a C7-30 alkylaryloxy group, and a C7-30 arylalkyloxy group.

[0218] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of halogen, hydrogen, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxide group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group.

[0219] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of halogen, hydrogen, and a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom.

[0220] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of halogen, hydrogen, and a C1-30 heteroatom containing hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom.

[0221] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of hydrogen and a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom.

[0222] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of hydrogen and a C1-30 heteroatom containing hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom.

[0223] In some embodiments, R7, R8, R9and R10are each hydrogen.

[0224] In embodiments of the disclosure, the bridged phosphinimine catalyst of formula II, is a bridged phosphinimine catalyst represented by formula IV : wherein M, R1, R2, R3, R4, R5, R6, and X1are as defined above for formulas I and II; and wherein G is a group 14 element; wherein R° and R°* are each independently selected from the group consisting of halogen; hydrogen; a Ci-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; wherein the groups of R° and R°* may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group of the formula -NR 2, a phosphide group of the formula -PR 2, a thiolate group of the formula -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein R7, R8, R9and R10are each independently selected from the group consisting of halogen; hydrogen; a Ci-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; an oxy group, -OR’; an amido group, -NR 2; a phosphide group, -PR 2; a thiolate group, -SR ; a silyl group of the formula -Si(Ra)3; and a germanyl group of the formula -Ge(Ra)3; wherein two adjacent groups of R7, R8, R9and R10may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group of the formula -NR 2, a phosphide group of the formula -PR 2, a thiolate group of the formula -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group; and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group.

[0225] In some embodiments G is carbon, C, or silicon, Si, or germanium, Ge.

[0226] In some embodiments G is carbon, C, or silicon, Si.

[0227] In some embodiments G is carbon, C.

[0228] In some embodiments G is silicon, Si.

[0229] In some embodiments G is germanium, Ge.

[0230] In some embodiments, R° and R°* are each independently selected from the group consisting of halogen, hydrogen, a C1-30 alkyl group, a C1-30 alkoxy group, a C7-30 alkylaryl group, a C7-30 arylalkyl group, a Ce-30 aryl group, a Ce-30 aryloxide group, a C7-30 alkylaryloxy group, and a C7-30 arylalkyloxy group. In some embodiments, R° and R°* are each independently selected from the group consisting of halogen, hydrogen, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxide group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group.

[0231] In embodiments, R° and R°* are each independently selected from the group consisting of hydrogen, a C1-20 alkyl group and a C6-20 aryl group.

[0232] In embodiments, R° and R°* are each independently a Ci-8 alkyl group.

[0233] In embodiments, R° and R°* are each independently a C6-20 aryl group.

[0234] In embodiments, R° is hydrogen and R°* is a Ci-8 alkyl group.

[0235] In embodiments, R° is hydrogen and R°* is a Ce-20 aiyl group.

[0236] In embodiments, R° is hydrogen and R°* is a methyl group.

[0237] In embodiments, R° is hydrogen and R°* is a phenyl group.

[0238] In embodiments, R° and R°* are each hydrogen.

[0239] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of halogen; hydrogen; a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; and a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; where two adjacent groups of R7, R8, R9and R10may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group, -NR 2, a phosphide group, -PR 2, a thiolate group, -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group and wherein each Rais independently selected from the group consisting of hydrogen, Ci-8 alkyl group, Ci-8 alkoxy group, Ce-20 aryloxy group, and Ce-20 aryl group.

[0240] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of halogen; hydrogen; and a Ci-so hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; where two adjacent groups of R7, R8, R9and R10may optionally be bonded to form a cyclic hydrocarbyl group, the cyclic hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group, -NR 2, a phosphide group, -PR 2, a thiolate group, -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group.

[0241] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of halogen; hydrogen; and a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; where two adjacent groups of R7, R8, R9and R10may optionally be bonded to form a cyclic heteroatom containing hydrocarbyl group, the cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, , an amido group, - NR 2, a phosphide group, -PR 2, a thiolate group, -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group and wherein each Rais independently selected from the group consisting of hydrogen, Ci-8 alkyl group, Ci-8 alkoxy group, Ce-20 aryloxy group, and Ce-20 aryl group.

[0242] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of halogen, hydrogen, a Ci-so alkyl group, a Ci-so alkoxy group, a C7-30 alkylaryl group, a C7-30 arylalkyl group, a Ce-30 aryl group, a Ce-30 aryloxide group, a C7-30 alkylaryloxy group, and a C7-30 arylalkyloxy group.

[0243] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of halogen, hydrogen, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxide group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group.

[0244] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of halogen, hydrogen, and a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom.

[0245] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of halogen, hydrogen, and a C1-30 heteroatom containing hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom.

[0246] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of hydrogen and a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom.

[0247] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of hydrogen and a C1-30 heteroatom containing hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom.

[0248] In some embodiments, R7, R8, R9and R10are each hydrogen.

[0249] In embodiments of the disclosure, the bridged phosphinimine catalyst of formula I, is a bridged phosphinimine catalyst represented by formula V : wherein M, R1, R2, X1and L are as defined above for formula I; and wherein R11, R12, R13, R14, R15, R16, R17, R18are each independently selected from the group consisting of halogen; hydrogen; a Ci-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; an oxy group, -OR’; an amido group, -NR 2; a phosphide group, -PR 2; a thiolate group, -SR ; a silyl group of the formula -Si(Ra)3; and a germanyl group of the formula -Ge(Ra)3; wherein two adjacent groups of R1R12, R13, R14, R15, R16, R17, R18may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group of the formula -NR 2, a phosphide group of the formula -PR 2, a thiolate group of the formula -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group; and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group.

[0250] In some embodiments, R11, R12, R13, R14, R15, R16, R17, R18are each independently selected from the group consisting of halogen; hydrogen; a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; and a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; where two adjacent groups of R11, R12, R13, R14, R15, R16, R17, R18may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group, -NR 2, a phosphide group, -PR 2, a thiolate group, -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C 1-20 alkyl group, and C6-20 aryl group and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group.

[0251] In some embodiments, R11, R12, R13, R14, R15, R16, R17and R18are each independently selected from the group consisting of halogen; hydrogen; and a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; where two adjacent groups of R11, R12, R13, R14, R15, R16, R17and R18may optionally be bonded to form a cyclic hydrocarbyl group, the cyclic hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group, -NR 2, a phosphide group, -PR 2, a thiolate group, -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group.

[0252] In some embodiments, R11, R12, R13, R14, R15, R16, R17and R18are each independently selected from the group consisting of halogen; hydrogen; and a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; where two adjacent groups of R11, R12, R13, R14, R15, R16, R17and R18may optionally be bonded to form a cyclic heteroatom containing hydrocarbyl group, the cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group, -NR 2, a phosphide group, -PR 2, a thiolate group, -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group. In some embodiments, R11, R12, R13, R14, R15, R16, R17, R18are each independently selected from the group consisting of halogen, hydrogen, a C1-30 alkyl group, a C1-30 alkoxy group, a C7-30 alkylaryl group, a C7-30 arylalkyl group, a Ce-30 aryl group, a Ce-30 aryloxide group, a C7-30 alkylaryloxy group, and a C7-30 arylalkyloxy group.

[0253] In some embodiments, R11, R12, R13, R14, R15, R16, R17, R18are each independently selected from the group consisting of halogen, hydrogen, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxide group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group.

[0254] In some embodiments, R11, R12, R13, R14, R15, R16, R17, R18are each independently selected from the group consisting of halogen, hydrogen, and a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom.

[0255] In some embodiments, R11, R12, R13, R14, R15, R16, R17, R18are each independently selected from the group consisting of halogen, hydrogen, and a C1-30 heteroatom containing hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom.

[0256] In some embodiments, R11, R12, R13, R14, R15, R16, R17, R18are each independently selected from the group consisting of hydrogen and a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom.

[0257] In some embodiments, R11, R12, R13, R14, R15, R16, R17, R18are each independently selected from the group consisting of hydrogen and a C1-30 heteroatom containing hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom.

[0258] In some embodiments, R12and R17are each independently an unsubstituted C1-30 hydrocarbyl group.

[0259] In some embodiments, R13and R16are each independently an unsubstituted C1-30 hydrocarbyl group.

[0260] In some embodiments, R12and R17are a C1-20 alkyl group.

[0261] In some embodiments, R13and R16are a C1-20 alkyl group.

[0262] In some embodiments, R12and R17are a C6-20 aryl group.

[0263] In some embodiments, R13and R16are a C6-20 aryl group.

[0264] In some embodiments, R12and R17are a tert-butyl group.

[0265] In some embodiments, R13and R16are a tert-butyl group. In some embodiments, R11, R13, R14, R15, R16and R18are each hydrogen.

[0266] In some embodiments, R11, R12, R14, R15, R17and R18are each hydrogen.

[0267] In some embodiments, R11, R12, R13, R14, R15, R16, R17and R18are each hydrogen.

[0268] In some embodiments, R11, R13, R14, R15, R16and R18are each hydrogen, and R12and R17are each independently an unsubstituted C1-30 hydrocarbyl group.

[0269] In some embodiments, R11, R13, R14, R15, R16and R18are each hydrogen, and R12and R17are each a tert-butyl group.

[0270] In some embodiments, R11, R12, R14, R15, R17and R18are each hydrogen, and R13and R16are each independently an unsubstituted C1-30 hydrocarbyl group.

[0271] In some embodiments, R11, R12, R14, R15, R17and R18are each hydrogen, and R13and R16are each a tert-butyl group.

[0272] In embodiments of the disclosure, the bridged phosphinimine catalyst of formula V, is a bridged phosphinimine catalyst represented by formula VI: wherein are as defined above for formulas I and V ; and wherein R7, R8, R9and R10are each independently selected from the group consisting of halogen; hydrogen; a Ci-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; an oxy group, -OR’; an amido group, -NR 2; a phosphide group, -PR 2; a thiolate group, -SR ; a silyl group of the formula -Si(Ra)3; and a germanyl group of the formula -Ge(Ra)3; wherein two adjacent groups of R7, R8, R9and R10may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group of the formula -NR 2, a phosphide group of the formula -PR 2, a thiolate group of the formula -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group; and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group.

[0273] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of halogen; hydrogen; a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; and a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; where two adjacent groups of R7, R8, R9and R10may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group, -NR 2, a phosphide group, - PR 2, a thiolate group, -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group.

[0274] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of halogen; hydrogen; and a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; where two adjacent groups of R7, R8, R9and R10may optionally be bonded to form a cyclic hydrocarbyl group, the cyclic hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group, -NR 2, a phosphide group, -PR 2, a thiolate group, -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group.

[0275] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of halogen; hydrogen; and a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; where two adjacent groups of R7, R8, R9and R10may optionally be bonded to form a cyclic heteroatom containing hydrocarbyl group, the cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, , an amido group, - NR 2, a phosphide group, -PR 2, a thiolate group, -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group.

[0276] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of halogen, hydrogen, a C1-30 alkyl group, a C1-30 alkoxy group, a C7-30 alkylaryl group, a C7-30 arylalkyl group, a C6-30 aryl group, a C6-30 aryloxide group, a C7-30 alkylaryloxy group, and a C7-30 arylalkyloxy group.

[0277] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of halogen, hydrogen, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxide group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group.

[0278] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of halogen, hydrogen, and a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom.

[0279] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of halogen, hydrogen, and a C1-30 heteroatom containing hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom.

[0280] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of hydrogen and a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom.

[0281] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of hydrogen and a C1-30 heteroatom containing hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom.

[0282] In some embodiments, R7, R8, R9and R10are each hydrogen. In some embodiments, R7, R8, R9and R10are each hydrogen; and R11, R12, R13, R14, R15, R16, R17, R18are each independently selected from the group consisting of halogen, hydrogen, a C1-30 alkyl group, and a Ce-so aryl group.

[0283] In some embodiments, R7, R8, R9and R10are each hydrogen; R11, R13, R14, R15, R16and R18are each hydrogen, and R12and R17are each independently a C1-20 alkyl group or a C6-20 aryl group.

[0284] In some embodiments, R7, R8, R9and R10are each hydrogen; R11, R13, R14, R15, R16and R18are each hydrogen, and R12and R17are each a tert-butyl group.

[0285] In some embodiments, R7, R8, R9and R10are each hydrogen; R11, R12, R14, R15, R17and R18are each hydrogen, and R13and R16are each independently a C1-20 alkyl group or a C6-20 aryl group.

[0286] In some embodiments, R7, R8, R9and R10are each hydrogen; R11, R12, R14, R15, R17and R18are each hydrogen, and R13and R16are each a tert-butyl group.

[0287] In embodiments of the disclosure, the bridged phosphinimine catalyst of formula VI, is a bridged phosphinimine catalyst represented by formula Via: wherein M, R1, R2, R12, R17and X1are as defined above for formulas I and V.

[0288] In embodiments of the disclosure, the bridged phosphinimine catalyst of formula VI, is a bridged phosphinimine catalyst represented by formula VIb:

[0289] wherein M, R1, R2and X1are as defined above for formula I.

[0290] In embodiments of the disclosure, the bridged phosphinimine catalyst of formula VI, is a bridged phosphinimine catalyst represented by formula IVc: wherein R1, R2, R12, R17and X1are as defined above for formulas I and V.

[0291] In embodiments of the disclosure, the bridged phosphinimine catalyst of formula VI, is a bridged phosphinimine catalyst represented by formula Vid: wherein R1, R2and X1are as defined above for formula I.

[0292] In embodiments of the disclosure, the bridged phosphinimine catalyst of formula VI, is a bridged phosphinimine catalyst represented by formula Vie:

[0293] wherein X1is as defined above for formula I.

[0294] In an embodiment of the disclosure, the bridged phosphinimine catalyst of formula

[0295] VI, is a bridged phosphinimine catalyst represented by formula VIf: (VIf).

[0296] In an embodiment of the disclosure, the bridged phosphinimine catalyst of formula VI, is a bridged phosphinimine catalyst represented by formula VIg: (VIg).

[0297] In an embodiment of the disclosure, the bridged phosphinimine catalyst of formula VI, is a bridged phosphinimine catalyst represented by formula VIh:

[0298] wherein M and X1are as defined above for formula I.

[0299] In an embodiment of the disclosure, the bridged phosphinimine catalyst of formula

[0300] VI, is a bridged phosphinimine catalyst plex represented by formula Vli: wherein M and X1are as defined above for formula I.

[0301] In embodiments of the disclosure, the bridged phosphinimine catalyst of formula V, is a bridged phosphinimine catalyst represented by formula VII:

[0302] wherein M, R1, R2, R11, R12, R13, R14, R15, R16, R17, R18, and X1are as defined above for formulas I and V ; and wherein G is a group 14 element; wherein R° and R°* are each independently selected from the group consisting of halogen; hydrogen; a Ci-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; wherein the groups of R° and R°* may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group of the formula -NR 2, a phosphide group of the formula -PR 2, a thiolate group of the formula -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein R7, R8, R9and R10are each independently selected from the group consisting of halogen; hydrogen; a Ci-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; an oxy group, -OR’; an amido group, -NR 2; a phosphide group, -PR 2; a thiolate group, -SR ; a silyl group of the formula -Si(Ra)3; and a germanyl group of the formula -Ge(Ra)3; wherein two adjacent groups of R7, R8, R9and R10may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group of the formula -NR 2, a phosphide group of the formula -PR 2, a thiolate group of the formula -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group; and wherein each Rais independently selected from the group consisting of hydrogen, Ci-8 alkyl group, Ci-8 alkoxy group, Ce-20 aryloxy group, and Ce-20 aryl group.

[0303] In some embodiments G is carbon, C, or silicon, Si, or germanium, Ge.

[0304] In some embodiments G is carbon, C, or silicon, Si.

[0305] In some embodiments G is carbon, C.

[0306] In some embodiments G is silicon, Si.

[0307] In some embodiments G is germanium, Ge.

[0308] In some embodiments, R° and R°* are each independently selected from the group consisting of halogen, hydrogen, a C1-30 alkyl group, a C1-30 alkoxy group, a C7-30 alkylaryl group, a C7-30 arylalkyl group, a Ce-30 aryl group, a Ce-30 aryloxide group, a C7-30 alkylaryloxy group, and a C7-30 arylalkyloxy group.

[0309] In some embodiments, R° and R°* are each independently selected from the group consisting of halogen, hydrogen, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxide group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group.

[0310] In embodiments, R° and R°* are each independently selected from the group consisting of hydrogen, a C1-20 alkyl group and a C6-20 aryl group.

[0311] In embodiments, R° and R°* are each independently a Ci-8 alkyl group.

[0312] In embodiments, R° and R°* are each independently a C6-20 aryl group.

[0313] In embodiments, R° is hydrogen and R°* is a Ci-8 alkyl group.

[0314] In embodiments, R° is hydrogen and R°* is a Ce-20 aiyl group.

[0315] In embodiments, R° is hydrogen and R°* is a methyl group.

[0316] In embodiments, R° is hydrogen and R°* is a phenyl group.

[0317] In embodiments, R° and R°* are each hydrogen.

[0318] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of halogen; hydrogen; a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; and a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; where two adjacent groups of R7, R8, R9and R10may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group, -NR 2, a phosphide group, -PR 2, a thiolate group, -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group.

[0319] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of halogen; hydrogen; and a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; where two adjacent groups of R7, R8, R9and R10may optionally be bonded to form a cyclic hydrocarbyl group, the cyclic hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group, -NR 2, a phosphide group, -PR 2, a thiolate group, -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group.

[0320] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of halogen; hydrogen; and a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; where two adjacent groups of R7, R8, R9and R10may optionally be bonded to form a cyclic heteroatom containing hydrocarbyl group, the cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, , an amido group, -NR 2, a phosphide group, -PR 2, a thiolate group, -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group.

[0321] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of halogen, hydrogen, a C1-30 alkyl group, a C1-30 alkoxy group, a C7-30 alkylaryl group, a C7-30 arylalkyl group, a C6-30 aryl group, a C6-30 aryloxide group, a C7-30 alkylaryloxy group, and a C7-30 arylalkyloxy group.

[0322] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of halogen, hydrogen, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxide group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group.

[0323] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of halogen, hydrogen, and a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom.

[0324] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of halogen, hydrogen, and a C1-30 heteroatom containing hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom.

[0325] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of hydrogen and a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom.

[0326] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of hydrogen and a C1-30 heteroatom containing hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom.

[0327] In some embodiments, R7, R8, R9and R10are each hydrogen. In some embodiments, R7, R8, R9and R10are each hydrogen; and R11, R12, R13, R14, R15, R16, R17, R18are each independently selected from the group consisting of halogen, hydrogen, a C1-30 alkyl group, and a Ce-so aryl group.

[0328] In some embodiments, R7, R8, R9and R10are each hydrogen; R11, R13, R14, R15, R16and R18are each hydrogen, and R12and R17are each independently a C1-20 alkyl group or a C6-20 aryl group.

[0329] In some embodiments, R7, R8, R9and R10are each hydrogen; R11, R13, R14, R15, R16and R18are each hydrogen, and R12and R17are each a tert-butyl group.

[0330] In some embodiments, R7, R8, R9and R10are each hydrogen; R11, R12, R14, R15, R17and R18are each hydrogen, and R13and R16are each independently a C1-20 alkyl group or a C6-20 aryl group.

[0331] In some embodiments, R7, R8, R9and R10are each hydrogen; R11, R12, R14, R15, R17and R18are each hydrogen, and R13and R16are each a tert-butyl group.

[0332] In embodiments of the disclosure, the bridged phosphinimine catalyst of formula VII, is a bridged phosphinimine catalyst represented by formula Vila: wherein M, R1, R2, R°. R°*. R12, R17and X1are as defined above for formulas I, V and VII.

[0333] In embodiments of the disclosure, the bridged phosphinimine catalyst of formula VII, is a bridged phosphinimine catalyst represented by formula Vllb:

[0334] wherein M, R1, R2, RQ, RQ* and X1are as defined above for formulas I and VII.

[0335] In embodiments of the disclosure, the bridged phosphinimine catalyst of formula

[0336] VII, is a bridged phosphinimine catalyst represented by formula Vile: wherein R1, R2, R°. R°*. R12, R17and X1are as defined above for formulas I, V and VII.

[0337] In embodiments of the disclosure, the bridged phosphinimine catalyst of formula VII, is a bridged phosphinimine catalyst represented by formula Vlld:

[0338] wherein R1, R2, RQ, RQ* and X1are as defined above for formulas I and VII.

[0339] In embodiments of the disclosure, the bridged phosphinimine catalyst of formula

[0340] VII, is a bridged phosphinimine catalyst represented by formula Vile: wherein R°. R°* and X1are as defined above for formulas I and VII.

[0341] In embodiments of the disclosure, the bridged phosphinimine catalyst of formula VII, is a bridged phosphinimine catalyst represented by formula Vllf:

[0342] (VIH). wherein R° and R°* are as defined above for formula VII.

[0343] In embodiments of the disclosure, the bridged phosphinimine catalyst of formula

[0344] VII, is a bridged phosphinimine catalyst represented by formula Vllg: wherein R° and R°* are as defined above for formula VII.

[0345] In an embodiment of the disclosure, the bridged phosphinimine catalyst of formula VII, is a bridged phosphinimine catalyst represented by formula Vllh:

[0346] (Vllh).

[0347] In an embodiment of the disclosure, the bridged phosphinimine catalyst of formula

[0348] VII, is a bridged phosphinimine catalyst represented by formula VIIi: (VIIi). In embodiments of the disclosure, the bridged phosphinimine catalyst of formula

[0349] VII, is a bridged phosphinimine catalyst represented by formula Vllj :

[0350] wherein X1is as defined above for formula I.

[0351] In embodiments of the disclosure, the bridged phosphinimine catalyst of formula I, is a bridged phosphinimine catalyst represented by formula VIII: wherein M, R1, R2, X1and L are as defined above for formula I; and wherein R23is selected from the group consisting of hydrogen; a Ci-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; and a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; wherein R19, R20, R21, R22, R24, R25, R26, and R27are each independently selected from the group consisting of halogen; hydrogen; a Ci-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; an oxy group, -OR’; an amido group, -NR 2; a phosphide group, -PR 2; a thiolate group, -SR ; a silyl group of the formula -Si(Ra)3; and a germanyl group of the formula -Ge(Ra)3; wherein two adjacent groups of R19, R20, R21, R22, R24, R25, R26, and R27may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group of the formula -NR 2, a phosphide group of the formula -PR 2, a thiolate group of the formula -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group; and wherein each Rais independently selected from the group consisting of hydrogen, Ci-8 alkyl group, Ci-8 alkoxy group, Ce-20 aryloxy group, and Ce-20 aryl group.

[0352] In some embodiments, R23is selected from the group consisting of a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group.

[0353] In some embodiments, R23is selected from the group consisting of a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group.

[0354] In some embodiments, R19, R20, R21, R22, R24, R25, R26, and R27are each independently selected from the group consisting of halogen; hydrogen; a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; and a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; where two adjacent groups of R19, R20, R21, R22, R24, R25, R26, and R27may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a Ce-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group, -NR 2, a phosphide group, -PR 2, a thiolate group, -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and Ce-20 aryl group and wherein each Rais independently selected from the group consisting of hydrogen, Ci-8 alkyl group, Ci-8 alkoxy group, Ce-20 aryloxy group, and Ce-20 aryl group.

[0355] In some embodiments, R19, R20, R21, R22, R24, R25, R26, and R27are each independently selected from the group consisting of halogen; hydrogen; and a Ci-so hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; where two adjacent groups of R19, R20, R21, R22, R24, R25, R26, and R27may optionally be bonded to form a cyclic hydrocarbyl group, the cyclic hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group, -NR 2, a phosphide group, -PR 2, a thiolate group, -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group.

[0356] In some embodiments, R19, R20, R21, R22, R24, R25, R26, and R27are each independently selected from the group consisting of halogen; hydrogen; and a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; where two adjacent groups of R19, R20, R21, R22, R24, R25, R26, and R27may optionally be bonded to form a cyclic heteroatom containing hydrocarbyl group, the cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group, -NR 2, a phosphide group, -PR 2, a thiolate group, -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group.

[0357] In some embodiments, R19, R20, R21, R22, R24, R25, R26, and R27are each independently selected from the group consisting of halogen, hydrogen, a C1-30 alkyl group, a Ci-30 alkoxy group, a C7-30 alkylaryl group, a C7-30 arylalkyl group, a Ce-30 aryl group, a C6-30 aryloxide group, a C7-30 alkylaryloxy group, and a C7-30 arylalkyloxy group.

[0358] In some embodiments, R19, R20, R21, R22, R24, R25, R26, and R27are each independently selected from the group consisting of halogen, hydrogen, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxide group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group.

[0359] In some embodiments, R19, R20, R21, R22, R24, R25, R26, and R27are each independently selected from the group consisting of halogen, hydrogen, and a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom.

[0360] In some embodiments, R19, R20, R21, R22, R24, R25, R26, and R27are each independently selected from the group consisting of halogen, hydrogen, and a C1-30 heteroatom containing hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom.

[0361] In some embodiments, R19, R20, R21, R22, R24, R25, R26, and R27are each independently selected from the group consisting of hydrogen and a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom.

[0362] In some embodiments, R19, R20, R21, R22, R24, R25, R26, and R27are each independently selected from the group consisting of hydrogen and a C1-30 heteroatom containing hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom.

[0363] In some embodiments, R20is an unsubstituted C1-30 hydrocarbyl group.

[0364] In some embodiments, R20is a C1-8 alkyl group.

[0365] In some embodiments, R19, R21, R22, R24, R25, R26, and R27are each hydrogen.

[0366] In some embodiments, R19, R20, R21, R22, R24, R25, R26, and R27are each hydrogen.

[0367] In some embodiments, R20is an unsubstituted C1-30 hydrocarbyl group, and R19, R21, R22, R24, R25, R26, and R27are each hydrogen. In some embodiments, R20is a Ci-s alkyl group, and R19, R21, R22, R24, R25, R26, and R27are each hydrogen.

[0368] In some embodiments, R20is a methyl group.

[0369] In some embodiments, R20is a phenyl group.

[0370] In some embodiments, R23is selected from the group consisting of hydrogen, a Ci-30 alkyl group, and a C6-20 aryl group.

[0371] In some embodiments, R23is selected from the group consisting of a C1-30 alkyl group, and a C6-20 aryl group.

[0372] In some embodiments, R23is an unsubstituted C1-30 hydrocarbyl group.

[0373] In some embodiments, R23is a C1-8 alkyl group.

[0374] In some embodiments, R23is a methyl group.

[0375] In some embodiments, R23is a phenyl group.

[0376] In some embodiments, R20and R23are each independently an unsubstituted C1-30 hydrocarbyl group, and R19, R21, R22, R24, R25, R26, and R27are each hydrogen.

[0377] In some embodiments, R20and R23are each independently a C1-8 alkyl group, and R19, R21, R22, R24, R25, R26, and R27are each hydrogen.

[0378] In some embodiments, R20and R23are each a methyl group, and R19, R21, R22, R24, R25, R26, and R27are each hydrogen.

[0379] In embodiments of the disclosure, the bridged phosphinimine catalyst of formula VIII, is a bridged phosphinimine catalyst represented by formula IX: wherein are as defined above for formulas I and VIII; and wherein R7, R8, R9and R10are each independently selected from the group consisting of halogen; hydrogen; a Ci-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; an oxy group, -OR’; an amido group, -NR 2; a phosphide group, -PR 2; a thiolate group, -SR ; a silyl group of the formula -Si(Ra)3; and a germanyl group of the formula -Ge(Ra)3; wherein two adjacent groups of R7, R8, R9and R10may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group of the formula -NR 2, a phosphide group of the formula -PR 2, a thiolate group of the formula -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group; and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group.

[0380] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of halogen; hydrogen; a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; and a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; where two adjacent groups of R7, R8, R9and R10may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group, -NR 2, a phosphide group, -PR 2, a thiolate group, -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group.

[0381] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of halogen; hydrogen; and a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; where two adjacent groups of R7, R8, R9and R10may optionally be bonded to form a cyclic hydrocarbyl group, the cyclic hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group, -NR 2, a phosphide group, -PR 2, a thiolate group, -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group and wherein each Rais independently selected from the group consisting of hydrogen, Ci-8 alkyl group, Ci-8 alkoxy group, Ce-20 aryloxy group, and Ce-20 aryl group.

[0382] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of halogen; hydrogen; and a heteroatom containing Ci-so hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; where two adjacent groups of R7, R8, R9and R10may optionally be bonded to form a cyclic heteroatom containing hydrocarbyl group, the cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group, -NR 2, a phosphide group, -PR 2, a thiolate group, -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group.

[0383] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of halogen, hydrogen, a C1-30 alkyl group, a C1-30 alkoxy group, a C7-30 alkylaryl group, a C7-30 arylalkyl group, a Ce-30 aryl group, a Ce-30 aryloxide group, a C7-30 alkylaryloxy group, and a C7-30 arylalkyloxy group.

[0384] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of halogen, hydrogen, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxide group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group.

[0385] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of halogen, hydrogen, and a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom.

[0386] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of halogen, hydrogen, and a C1-30 heteroatom containing hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom. In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of hydrogen and a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom.

[0387] In some embodiments, R7, R8, R9and R10are each independently selected from the group consisting of hydrogen and a C1-30 heteroatom containing hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom.

[0388] In some embodiments, R7, R8, R9and R10are each hydrogen.

[0389] In embodiments of the disclosure, the bridged phosphinimine catalyst of formula IX, is a bridged phosphinimine catalyst represented by formula IXa: wherein M, R1, R2, R20, R23and X1are as defined above for formulas I and VIII.

[0390] In embodiments of the disclosure, the organometallic complex of formula IX, is an organometallic complex represented by formula IXb: wherein R1, R2, R20, R23and X1are as defined above for formulas I and VIII. In embodiments of the disclosure, the bridged phosphinimine catalyst of formula IX, is a bridged phosphinimine catalyst represented by formula IXc: wherein R20, R23and X1are as defined as above for formulas I and VIII. In embodiments of the disclosure, the bridged phosphinimine catalyst of formula IX, is a bridged phosphinimine catalyst represented by formula IXd: wherein X1is as defined above for formula I.

[0391] In an embodiment of the disclosure, the bridged phosphinimine catalyst of formula IX, is a bridged phosphinimine catalyst represented by formula IXe:

[0392] (IXe).

[0393] In an embodiment of the disclosure, the bridged phosphinimine catalyst of formula

[0394] IX, is a bridged phosphinimine catalyst represented by formula IXf: (IXf). In an alternate embodiment of the disclosure, a bridged phosphinimine catalyst is represented by formula X: wherein M, R1, R2, Cy and X1are as defined above for formula I; and

[0395] L* is a bridging group containing at least one cycloalkylene, heterocycloalkylene, arylene or heteroarylene group. The term “cycloalkylene” refers to a bivalent group containing a cycloaliphatic ring. The term “heterocycloalkylene” refers to a bivalent group containing a heterocycloaliphatic ring. The term “arylene” refers to a bivalent group containing an aromatic ring. The term “heteroarylene” refers to a bivalent group containing a heteroaromatic ring.

[0396] In some embodiments L* is a bridging group containing at least one arylene or heteroarylene group.

[0397] In some embodiments L* is a bridging group containing at least one arylene group. In some embodiments L* is a bridging group containing at least one phenylene group.

[0398] In some embodiments L* is a bridging group comprising up to 50 atoms selected from carbon atoms, hydrogen atoms and heteroatoms and containing at least one arylene or heteroarylene group. In some embodiments L* is a bridging group comprising up to 50 atoms selected from carbon atoms, hydrogen atoms and heteroatoms and containing at least one arylene group. In some embodiments L* is a bridging group comprising up to 50 atoms selected from carbon atoms, hydrogen atoms and heteroatoms and containing at least one phenylene group. In some embodiments L* is a bridging group comprising up to 50 atoms selected from carbon atoms and hydrogen atoms and containing at least one phenylene group.

[0399] The arylene or heteroarylene group within L* may be directly or indirectly covalently bound to P. The arylene or heteroarylene group within L* may be directly covalently bound to P (i.e., there may be a covalent bond from P to an atom of the ring of the arylene or heteroarylene group). Alternatively, the arylene or heteroarylene group within L may be indirectly covalently bound to P (i.e., there may be a further bivalent group between P and an atom of the ring of the arylene or heteroarylene group). The further bivalent group may be a hydrocarbylene group, for example an alkylene group or alkenylene group, or may be a bivalent group containing one or more heteroatoms.

[0400] The arylene or heteroarylene group within L* may be directly or indirectly covalently bound to Cy. The arylene or heteroarylene group within L* may be directly covalently bound to Cy (i.e., there may be a covalent bond from P to an atom of the ring of the arylene or heteroarylene group). Alternatively, the arylene or heteroarylene group within L may be indirectly covalently bound to Cy (i.e., there may be a further bivalent group between Cy and an atom of the ring of the arylene or heteroarylene group). The further bivalent group may be a hydrocarbylene group, for example an alkylene group or alkenylene group, or may be a bivalent group containing one or more heteroatoms. In some embodiments, L* contains a contiguous chain of 4 atoms or fewer connecting P with Cy. In some embodiments, L* contains a contiguous chain of 3 atoms or fewer connecting P with Cy. In some embodiments, L* contains a contiguous chain of 3 atoms connecting P with Cy. In some embodiments, L* contains a contiguous chain of 2 atoms connecting P with Cy.

[0401] In some embodiments, L* contains a contiguous chain of atoms connecting P with Cy, wherein the two ortho carbon atoms of the phenylene group form part of the contiguous chain of atoms.

[0402] In some embodiments L* is selected from: wherein Ttr vvv' indicates the point of attachment to P and (*) indicates the point of attachment to Cy; each RG* is independently selected from halogen and unsubstituted C1-12 alkyl; and RK* and RL* are each independently selected from hydrogen, unsubstituted C1-12 alkyl group, and unsubstituted or substituted C6-20 aryl group.

[0403] In embodiments RK* and RL* are each independently selected unsubstituted C1-12 alkyl group, and unsubstituted or substituted C6-20 aryl group.

[0404] In some embodiments RG* is absent (the phenylene group, or the biphenylene group, or the naphthalene group is unsubstituted).

[0405] In some embodiments RK* and RL* are each hydrogen.

[0406] The Unbridged Phosphinimine Catalyst

[0407] An unbridged phosphinimine catalyst, is, in the present invention, a group 4 metal based (e.g. Ti, Zr, or Hf) single site olefin polymerization catalyst which has two activatable ligands, a cyclopentadienyl-type ligand and a phosphinimine ligand in which the cyclopentadienyl-type ligand and the phosphinimine ligand are not connected by a bridging group.

[0408] The use of any unbridged phosphinimine catalyst is contemplated for use in embodiments of the present disclosure and some non-limiting examples of unbridged phosphinimine catalysts which may be useful in embodiments of the disclosure can be found in U.S. Pat. Nos. 6,063,879; 6,235,672; 6,277,931; 6,342,463; 6,372,864; 6,777,509; 6,984,695 and 8,431,657, each of which are incorporated herein by reference.

[0409] In an embodiment, an unbridged phosphinimine catalyst has the formula XI: (Cy^aM^PIMX1^ (XI) wherein (Cyu) represents is an unbridged cyclopentadienyl-type ligand, one which is not covalently attached to the phosphinimine ligand, PI; Murepresents a metal atom selected from the group consisting of Ti, Zr, and Hf; PI represents a phosphinimine ligand, one which is not covalently attached to the cyclopentadienyl ligand, Cyu; X1represents an activatable ligand as already defined above for a bridged phosphinimine catalyst having the formula I; a is 0 or 1; b is 1 or 2; (a+b) = 2; n is 1 or 2, and; the sum of (a+b+n) equals the valance of the metal Mu.

[0410] As used in the present disclosure, “Cyu” represents an unbridged “cyclopentadienyl- type ligand” which contains within its structure a cyclopentadienyl moiety, which refers to a 5 -member carbon ring and which can coordinate to a metal centre through de localized 71-bonding, or in some cases through o-bonding.

[0411] In some embodiments, “Cyu” represents an unbridged “cyclopentadienyl-type ligand” which contains within its structure a cyclopentadienyl moiety, which refers to a 5 -member carbon ring having delocalized n-bonding within the ring (e.g., aromaticity) and which can coordinate to a metal centre.

[0412] As used herein, the term “cyclopentadienyl-type ligand” is meant to include ligands which contain at least one five-carbon ring which is bonded to the metal via eta-5 (or in some cases eta-3, or in some cases eta-1) bonding. Thus, the term “cyclopentadienyl-type ligands” includes, for example, unsubstituted cyclopentadienyl, singly or multiply substituted cyclopentadienyl, unsubstituted indenyl, singly or multiply substituted indenyl, unsubstituted fluorenyl and singly or multiply substituted fluorenyl. Hydrogenated versions of indenyl and fluorenyl ligands are also contemplated for use in the current disclosure, so long as the five-carbon ring which bonds to the metal via eta-5 (or in some cases eta-3, or eta-1) bonding remains intact.

[0413] In an embodiment Cyuis selected from the group consisting of unsubstituted cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl, substituted indenyl, unsubstituted fluorenyl and substituted fluorenyl.

[0414] In embodiments of the disclosure, substituents for a cyclopentadienyl ligand, an indenyl ligand (or hydrogenated version thereof) and a fluorenyl ligand (or hydrogenated version thereof) may be selected from the group consisting of a C1-30 hydrocarbyl group, which hydrocarbyl group may be unsubstituted or further substituted by for example a halogen (such as would be the case for a pentafluorobenzyl group, -CH2C6F5), a C1-20 alkoxy group, a C6-20 aryl group, a C6-20 aryloxy group (each of which may be further substituted by for example a halogen); an amido group which is unsubstituted or substituted by up to two C1-8 alkyl groups; a phosphide group which is unsubstituted or substituted by up to two C1-8 alkyl groups; a silyl group of the formula -Si(Ra)3 wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group and C6-20 aryl group; and a germanyl group of the formula - Ge(Ra)s wherein Rais as defined directly above.

[0415] In some embodiments, Cyuis selected from the group consisting of heteroatom substituted cyclopentadienyl-type ligands, and heteroatom containing cyclopentadienyl-type ligands.

[0416] In some embodiments, Cyuis selected from the group consisting of unsubstituted or substituted cyclopentadienyl ligands; unsubstituted or substituted cyclopentenophenanthryl ligands and hydrogenated versions thereof; unsubstituted or substituted indenyl ligands and hydrogenated versions thereof; unsubstituted or substituted fluorenyl ligands and hydrogenated versions thereof; unsubstituted or substituted octahydrofluorenyl ligands; and unsubstituted or substituted azulenyl ligands.

[0417] In some embodiments, Cyuis a cyclopentadienyl ligand which is unsubstituted or substituted by up to five substituents independently selected from the group consisting of halogen; a Ci-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; an oxy group, -OR’; an amido group, -NR 2; a phosphide group, -PR 2; a thiolate group, -SR ; a silyl group of the formula -Si(Ra)3; and a germanyl group of the formula -Ge(Ra)3; wherein two adjacent substituents on the cyclopentadienyl ligand may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group of the formula -NR 2, a phosphide group of the formula -PR 2, a thiolate group of the formula -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group; and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group. In some embodiments, Cyuis an indenyl ligand which is unsubstituted or substituted by up to seven substituents independently selected from the group consisting of halogen; a Ci-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; an oxy group, -OR’; an amido group, -NR 2; a phosphide group, -PR 2; a thiolate group, -SR ; a silyl group of the formula -Si(Ra)3; and a germanyl group of the formula -Ge(Ra)3; wherein two adjacent substituents on the indenyl ligand may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group of the formula -NR 2, a phosphide group of the formula -PR 2, a thiolate group of the formula -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group; and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group.

[0418] In some embodiments, Cyuis an fluorenyl ligand which is unsubstituted or substituted by up to nine substituents independently selected from the group consisting of halogen; a Ci-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; a heteroatom containing C1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; an oxy group, -OR’; an amido group, -NR 2; a phosphide group, -PR 2; a thiolate group, -SR ; a silyl group of the formula -Si(Ra)3; and a germanyl group of the formula -Ge(Ra)3; wherein two adjacent substituents on the fluorenyl ligand may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, a C7-20 arylalkyloxy group, an amido group of the formula -NR 2, a phosphide group of the formula -PR 2, a thiolate group of the formula -SR , a silyl group of the formula -Si(Ra)3, and a germanyl group of the formula -Ge(Ra)3; wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group; and wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group, and C6-20 aryl group.

[0419] In an embodiment, the unbridged cyclopentadienyl-type ligand, Cyuis a cyclopentadienyl ligand, Cp (i.e. CsHs').

[0420] In an embodiment the phosphinimine ligand, PI, is defined by formula:

[0421] (RP)3P = N - wherein the Rpgroups are each independently selected from the group consisting of a hydrogen atom; a halogen atom; a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom, C1-20 alkyl group, C1-20 alkoxy group, C7-20 alkylaryl group, C7-20 arylalkyl group, C6-20 aryl group, C6-20 aryloxy group, C7-20 alkylaryloxy group, and / or C7-20 arylalkyloxy group; an amido group of the formula -NR’2; a silyl group of the formula -Si(Ra)3; a germanyl group of the formula -Ge(Ra)3; and a phosphinimine group of the formula -N=P(Rb)(Rc)(Rd); wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group; wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group and C6-20 aryl group; and Rb, Rc, Rd, are each independently a C1-20 alkyl group.

[0422] In an embodiment each Rpis a C1-20 alkyl group group.

[0423] In an embodiment each Rpis a tert-butyl group.

[0424] In an embodiment each Rpis an isopropyl group.

[0425] In an embodiment of the disclosure, the metal, Muin the unbridged phosphinimine catalyst is titanium, Ti.

[0426] In an embodiment of the disclosure, the unbridged phosphinimine catalyst is cyclopentadienyl tri(tertiarybutyl)phosphinimine titanium dichloride, Cp((t-Bu)3PN)TiCh.

[0427] In an embodiment of the disclosure, the unbridged phosphinimine catalyst is cyclopentadienyl tri(tertiarybutyl)phosphinimine titanium dimethide, Cp((t-Bu)3PN)TiMe2. Catalyst Activation

[0428] A person skilled in the art will know that most single site catalysts, such as bridged or unbridged phosphinimine catalysts typically require activation using suitable catalyst activators and / or cocatalytic compounds in order to effect the polymerization of olefins with high activity. Without wishing to be bound by theory, catalyst activators generate an active “cationic” metal center, by way of removing an activatable ligand from the metal center of a pre-polymerization catalyst (by for example, protonolysis, or by electrophilic abstraction). Accordingly, single site catalysts, such as the bridged and unbridged phosphinimine catalysts disclosed herein may also referred to as “pre-polymerization catalysts”.

[0429] In addition to the single site catalyst molecule per se (e.g. the bridged phosphinimine catalyst and / or unbridged phosphinimine catalyst), an active single site polymerization catalyst may further comprise one or more than one catalyst activator (also known as a “cocatalyst”) used to activate the pre-polymerization catalyst and which can be any suitable catalyst activator (or co-catalyst) known to persons skilled in the art, including one or more catalyst activator(s) selected from the group consisting of the so-called ionic activators, which includes boron-based activators; alkylaluminoxanes; and organoaluminum compounds.

[0430] A catalyst activator may optionally be used together with an alkylating agent, which are also well known in the art and includes alkylaluminoxane compounds, organoaluminum compounds and dialkyl zinc compounds.

[0431] Boron-based catalyst activators, also known as “ionic activators”, are well known to persons skilled in the art. Alkylaluminoxanes which may also serve as catalyst activators or co-catalysts are likewise well known to persons skilled in the art.

[0432] Without wishing to be bound by theory, aluminum-based species such as alkylaluminoxanes, and organoaluminum compounds may act as catalyst activators per se, and / or as alkylating agents and / or as scavenging compounds (e.g., they react with species which adversely affect the polymerization activity of the single site catalyst, and which may be present in a polymerization reactor).

[0433] The active single site polymerization catalyst may in some embodiments further comprise a hindered phenol compound.

[0434] Without wishing to be bound by theory, the alkylaluminoxanes used in the present disclosure are complex aluminum compounds of the formula: R2Al1O(RAl1O)mAl1R2, wherein each Ris independently selected from the group consisting of C1-20 hydrocarbyl radicals and m is from 3 to 50.

[0435] In an embodiment of the disclosure, R of the alkylaluminoxane, is a methyl radical and m is from 10 to 40.

[0436] The alkylaluminoxanes are typically used in substantial molar excess compared to the amount of group 4 transition metal in the single site catalyst (e.g the bridged and / or unbridged phosphinimine catalyst). In embodiments, the Al / group 4 transition metal molar ratios may be from about 5: 1 to about 10,000: 1, or from about 10: 1 to about 1000: 1, or from about 30: 1 to about 500: 1.

[0437] A person skilled in the art will know that the amount of alkylaluminoxane used relative to the group 4 transition metal in the single site catalyst can be optimized in order to remove (or titrate out) impurities present in a polymerization process. In some embodiments, the Al / group 4 transition metal molar ratio is optimized to maximize single site catalyst activity and may be in the range of from about 0.1 : 1 to greater than 100: 1 or higher than 100: 1. In an embodiment of the disclosure, the alkylaluminoxane co-catalyst is methylaluminoxane (MAO).

[0438] In an embodiment of the disclosure, the alkylaluminoxane co-catalyst is modified methylaluminoxane (MMAO).

[0439] It is well known in the art, that alkylaluminoxanes can serve multiple roles as a catalyst alkylator, a catalyst activator, and a scavenger. Hence, an alkylaluminoxane activator is often used in combination with activatable ligands such as halogens.

[0440] In embodiments, the boron-based catalyst activator (which in some embodiments is also known as an “ionic activator”) may be selected from the group consisting of: (i) compounds of the formula [R34]+[B(R35)4]‘ wherein B is a boron atom, R34is a cyclic C5-7 aromatic cation or a triphenyl methyl cation and each R35is independently selected from the group consisting of phenyl groups which are unsubstituted or substituted with from 3 to 5 substituents selected from the group consisting of a fluorine atom, a C1-4 alkyl or alkoxy group which is unsubstituted or substituted by a fluorine atom; and a silyl group of the formula — Si— (R*)s; wherein each R* is independently selected from the group consisting of a hydrogen atom and a C1-4 alkyl group; and (ii) compounds of the formula [(R36)tZH]+[B(R35)4]- wherein B is a boron atom, H is a hydrogen atom, Z is a nitrogen atom or phosphorus atom, t is 2 or 3 and R36is selected from the group consisting of C1-30 alkyl groups, a phenyl group which is unsubstituted or substituted by up to three C1-4 alkyl groups, or one R36taken together with a nitrogen atom may form an anilinium group and R35is as defined above; and (iii) compounds of the formula B(R35)s wherein R35is as defined above, and adducts thereof, for example, hydrosilane-B(CeF5)3.

[0441] In some embodiments, in the above compounds, preferably R35is a pentafluorophenyl group, and R34is a triphenylmethyl cation, Z is a nitrogen atom and R36is a C1-4 alkyl group or one R36taken together with a nitrogen atom forms an anilinium group (e.g., PhR362NH+, which is substituted by two R36groups such as for example two C1-4 alkyl groups).

[0442] Examples of boron-based catalyst activator compounds capable of ionizing a single site catalyst and which may be used in embodiments of the disclosure include the following: triethylammonium tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron, tri(n- butyl)ammonium tetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron, tributylammonium tetrakis(pentafluorophenyl)boron, tripropylammonium tetrakis(o,p-dimethylphenyl)boron, tributylammonium tetrakis(m,m-dimethylphenyl)boron, tributylammonium tetrakis(p- trifluoromethylphenyl)boron, tributylammonium tetrakis(pentafluorophenyl)boron, tri(n- butyl)ammonium tetra (o-tolyl)boron, N,N-dimethylanilinium tetra(phenyl)boron, N,N- diethylanilinium tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)n-butylboron, N,N- 2,4,6-pentamethylanilinium tetra(phenyl)boron, di-(isopropyl)ammonium tetrakis(pentafluorophenyl)boron, dicyclohexylammonium tetra(phenyl)boron, triphenylphosphonium tetra(phenyl)boron, tri(methylphenyl)phosphonium tetra(phenyl)boron, tri(dimethylphenyl)phosphonium tetra(phenyl)boron, tropylium tetrakis(pentafluorophenyl) borate, triphenylmethylium tetrakispentafluorophenyl borate, benzene (diazonium) tetrakis(pentafluorophenyl) borate, tropylium phenyltris- (pentafluorophenyl) borate, triphenylmethylium phenyl-tris(pentafluorophenyl) borate, benzene (diazonium) phenyltris(pentafluorophenyl) borate, tropylium tetrakis (2, 3,5,6- tetrafluorophenyl) borate, triphenylmethylium tetrakis(2,3,5,6-tetrafluorophenyl) borate, benzene (diazonium) tetrakis(3,4,5-trifluorophenyl) borate, tropylium tetrakis(3,4,5- trifluorophenyl) borate, benzene (diazonium) tetrakis(3, 4, 5 -trifluorophenyl) borate, tropylium tetrakis(l,2,2-trifluoroethenyl) borate, triphenyhnethylium tetrakis( 1,2,2- trifluoroethenyl ) borate, benzene (diazonium) tetrakis(l,2,2-trifluoroethenyl) borate, tropylium tetrakis(2,3,4,5-tetrafluorophenyl) borate, triphenylmethylium tetrakis(2, 3,4,5- tetrafluorophenyl) borate, and benzene (diazonium) tetrakis(2, 3, 4, 5 -tetrafluorophenyl) borate.

[0443] Further specific examples of boron-based catalyst activator compounds capable of activating (i.e. ionizing) a single site catalyst and which may be used in embodiments of the present disclosure are disclosed in U.S. Pat. Nos 5,919,983, 6,121,185, 10,730,964 and 11,041,031. The boron-based catalyst activator, [(hydrogenated tallow alkyl)2(Me)NH][B(C6Fs)4] is also known as “bis(hydrogenated-tallowalkyl) methylammonium tetrakis(pentafluorophenyl)borate” and has the formula: [(C18-22H37-45)2(Me)NH] [B(C6F5)4] .

[0444] In embodiments of the disclosure, the boron-based catalyst activator comprises [(hydrogenated tallow alkyl)2(Me)NH][B(C6Fs)4; and / or N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate (“[Me2NHPh][B(C6Fs)4]”); and / or triphenylmethylium tetrakis(pentafluorophenyl) borate (“[Ph3C][B(C6Fs)4]”); and / or tris(pentafluorophenyl) boron.

[0445] In embodiments of the disclosure, the boron-based catalyst activator comprises [(hydrogenated tallow alkyl)2(Me)NH] [B(CeF5)4; or N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate (“[Me2NHPh][B(C6Fs)4]”), or triphenylmethylium tetrakis(pentafluorophenyl) borate (“[Ph3C][B(C6Fs)4]”), or tris(pentafluorophenyl) boron.

[0446] In embodiments of the disclosure, the boron-based catalyst activator comprises N,N- dimethylanilinium tetrakis(pentafluorophenyl) borate (“[Me2NHPh][B(CeF5)4]”), and / or triphenylmethylium tetrakis(pentafluorophenyl) borate (“[Ph3C][B(CeF5)4]”), and / or tris(pentafluorophenyl) boron.

[0447] In embodiment of the disclosure, the boron-based catalyst activator comprises N,N- dimethylanilinium tetrakis(pentafluorophenyl) borate (“[Me2NHPh][B(CeF5)4]”), or triphenylmethylium tetrakis(pentafluorophenyl) borate (“[Ph3C][B(CeF5)4]”), or tris(pentafluorophenyl) boron.

[0448] In an embodiment of the disclosure, the boron-based catalyst activator comprises an ionic activator selected from the group consisting of [(hydrogenated tallow alkyl)2(Me)NH][B(CeF5)4; N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate (“[Me2NHPh][B(CeF5)4]”), and triphenylmethylium tetrakis(pentafluorophenyl) borate (“[Ph3C][B(C6F5)4]”).

[0449] In an embodiment of the disclosure, the boron-based catalyst activator is N,N- dimethylanilinium tetrakis(pentafluorophenyl) borate (“[Me2NHPh][B(CeF5)4]”).

[0450] In an embodiment of the disclosure, the boron-based catalyst activator is triphenylmethylium tetrakis(pentafluorophenyl) borate (“[Ph3C][B(CeF5)4]”).

[0451] In an embodiment of the disclosure, the boron-based catalyst activator is [(hydrogenated tallow alkyl)2(Me)NH][B(CeF5)4.

[0452] In an embodiment of the disclosure, the boron-based catalyst activator is trihydrocarbylammonium tetrakis(pentafluorophenyl) borate ([RZ3NH][B(CeF5)4], where each Rzis independently a Ci-40 branched alkyl group, a Ci-40 linear alkyl group, or a Ce-3o aryl group, wherein each of the branched alkyl group, the linear alkyl group, or the aryl group is unsubstituted or further substituted by one or more halogen, C1-30 alkyl group, C6-20 aryl group, C6-20 aryloxide group, C7-20 alkylaryloxy group, and / or C7-20 arylalkyloxy group.

[0453] In embodiments, the boron-based catalyst activator may be used in amounts which provide a molar ratio of group 4 transition metal (e.g. titanium in the bridged and / or unbridged phosphinimine catalyst) to boron that will be from about 1:0.5 to about 1: 10, or from about 1: 1 to about 1:6.

[0454] Optionally, in embodiments of the disclosure, the active single site polymerization catalyst may further include an organoaluminum compound defined by the formula: Al(R37)m(OR38)n(X¥)p wherein R37and R38are each independently Ci to C20 hydrocarbyl groups; X¥is a halide; m + n + p = 3; and m > 1.

[0455] In an embodiment of the disclosure, the organoaluminum compound used is defined by the formula:

[0456] Al(R37)x(OR38)ywherein x is from 1 to 3, x + y = 3, R37is a Ci to C10 hydrocarbyl group, and R38is an alkyl or an aryl group.

[0457] In an embodiment of the disclosure, the organoaluminum compound used is defined by the formula:

[0458] A1(R37)3wherein R37is a Ci to C20 hydrocarbyl group.

[0459] In an embodiment of the disclosure, the organoaluminum compound used is defined by the formula:

[0460] A1(R37)3wherein R37is a C6-20 aryl group, which aryl group is unsubstituted or substituted with one or more than one fluorine.

[0461] In particular embodiments, organoaluminum compounds can be selected from the group consisting of triethylaluminum, triisobutyl aluminum, tri-n-octylaluminum, diethyl aluminum ethoxide and mixtures thereof.

[0462] Optionally, in embodiments of the disclosure, the active single site polymerization catalyst may further include a dialkyl zinc compound defined by the formula:

[0463] Zn(R39)2wherein each R39is independently a Ci to C20 alkyl group.

[0464] Optionally, in embodiments of the disclosure, the active single site polymerization catalyst may further include a hindered phenol compound.

[0465] In embodiments of the present disclosure, a hindered phenol compound is used in combination with a single site catalyst (e.g. a bridged or unbridged phosphinimine catalyst), and an alkylaluminoxane co-catalyst. In embodiments of the present disclosure, a hindered phenol compound is used in combination with a single site catalyst, an alkylaluminoxane co-catalyst and an organoaluminum compound. In embodiments of the present disclosure, a hindered phenol compound is used in combination with a single site catalyst, a boron-based catalyst activator and an alkylaluminoxane co-catalyst. In embodiments of the present disclosure, a hindered phenol compound is used in combination with a single site catalyst, a boron-based catalyst activator, an alkylaluminoxane co-catalyst and an organoaluminum compound. In embodiments of the present disclosure, a hindered phenol compound is used in combination with a single site catalyst, a boron-based catalyst activator, an alkylaluminoxane co-catalyst, an organoaluminum compound and a dialkyl zinc compound.

[0466] Generally, hindered phenol compounds (or “sterically hindered” phenol compounds) are phenols having one or more bulky substituent, such as a sterically bulky hydrocarbyl group, non-limited examples of which include a tert-butyl group and a 1-adamantyl group.

[0467] In embodiments of the disclosure, a hindered phenol compound, will have a sterically bulky hydrocarbyl group on at least one or both of the carbon atoms adjacent to the carbon atom bonded to a hydroxy group (e.g., a bulky hydrocarbyl group is located at one or both of the 2 and 6 locations of a hindered phenol moiety).

[0468] In embodiments of the disclosure, a hindered phenol compound, comprises a 2,6- dihydrocarbyl group substituted hindered phenol moiety.

[0469] In embodiments of the disclosure, a hindered phenol compound comprises a 2,6- dihydrocarbyl group substituted hindered phenol moiety, which moiety is further optionally substituted at one or more of the 3, 4 and 5 locations with a hydrocarbyl group or a heteroatom containing hydrocarbyl group.

[0470] Non-limiting examples of hindered phenol compounds which may be employed in embodiments of the present disclosure include butylated phenolic antioxidants, butylated hydroxytoluene; 2,6-di-tertiarybutyl-4-ethyl phenol (“BHEB”); 4,4'-methylenebis (2,6-di- tertiary-butylphenol); l,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl)benzene and octadecyl-3 -(3 ',5 '-di -tert-butyl -4'-hydroxyphenyl) propionate .

[0471] In embodiments, a hindered phenol compound is present in an amount which provides a molar ratio of aluminum from an alkylaluminoxane co-catalyst to the hindered phenol compound (i.e., the ratio of Al ^hindered phenol compound) of from about 1: 1 to about 10 : 1 , or from about 2 : 1 to about 5: 1.

[0472] Optionally, in embodiments, a hindered phenol compound is added to an alkylaluminoxane co-catalyst or added to an organoaluminum compound prior to contact of the alkylaluminoxane or the organoaluminum compound with one or more other components of the active single site polymerization catalyst.

[0473] In embodiments of the disclosure, in order to produce an active single site polymerization catalyst, the quantity and mole ratios of several catalyst components: the single site catalyst (e.g. the bridged and / or unbridged phosphinimine pre-polymerization catalyst), the alkylaluminoxane co-catalyst, the boron-based activator, the optional organoaluminum compound, the optional dialkyl zinc compound, and the optional hindered phenol are optimized.

[0474] In embodiments of the disclosure, in addition to feeding a bridged phosphinimine catalyst molecule per se and an unbridged phosphinimine catalyst molecule per se to a polymerization reactor, one or more than one catalyst activator is also fed to the polymerization reactor, individually, or in any combination, and the one or more than one catalyst activator, individually, or in any combination may be fed directly to the polymerization reactor or may be combined, individually, or in any combination with the bridged phosphinimine catalyst molecule per se and / or the unbridged phosphinimine catalyst molecule per se, upstream of, and on route to the polymerization reactor.

[0475] In embodiments of the disclosure, in addition to feeding a bridged phosphinimine catalyst molecule per se and an unbridged phosphinimine catalyst molecule per se to a polymerization reactor, one or more than one of the following further components, (a) through (e), may also be fed to the polymerization reactor, individually, or in any combination, and these further components, (a) through (e), individually, or in any combination may be fed directly to the polymerization reactor or they may be combined, individually, or in any combination with the bridged phosphinimine catalyst molecule per se and / or the unbridged phosphinimine catalyst molecule per se, upstream of, and on route to the polymerization reactor: a) a boron-based catalyst activator; b) an alkylaluminoxane co-catalyst; c) an organoaluminum compound; d) a dialkylzinc compound; e) a hindered phenol compound.

[0476] In embodiments of the disclosure, in addition to feeding a bridged phosphinimine catalyst molecule per se and an unbridged phosphinimine catalyst molecule per se to a polymerization reactor, one or more than one catalyst activator or cocatalyst as defined above, and optionally a hindered phenol compound, are fed to the polymerization reactor. In an embodiment, in addition to feeding a bridged phosphinimine catalyst molecule per se and an unbridged phosphinimine catalyst molecule per se to a polymerization reactor, a boron-based catalyst activator, an alkylaluminoxane co-catalyst, and optionally a hindered phenol compound, are fed to the polymerization reactor. In an embodiment, in addition to feeding a bridged phosphinimine catalyst molecule per se and an unbridged phosphinimine catalyst molecule per se to a polymerization reactor, a boron-based catalyst activator, an alkylaluminoxane co-catalyst, and a hindered phenol compound are fed to the polymerization reactor.

[0477] Polymerization Process

[0478] The present mixed polymerization catalyst system is contemplated for use in any polymerization process type and reactor, including, solution phase, slurry phase, and gas phase polymerization processes carried out in any appropriate and corresponding reactor type such as, for example, a tank reactor, a loop reactor, a fluidized bed reactor, and a tubular reactor. In an embodiment, the present mixed polymerization catalyst system is used in a solution phase polymerization process and appropriate solution phase polymerization reactor such as, for example a continuously stirred tank reactor, or a tubular reactor. In an embodiment, the present mixed polymerization catalyst system is used in a continuous solution phase polymerization process and appropriate continuous solution phase polymerization reactor such as, for example a continuously stirred tank reactor, or a tubular reactor.

[0479] In embodiments, a molar ratio of a bridged phosphinimine catalyst to an unbridged phosphinimine catalyst fed to or present in a polymerization reactor is from 1 : 99 to 99: 1, or from 5:95 to 95:5, or from 10:90 to 90: 10, or from 20:80 to 80:20, or from 25:75 to 75:25, or from 30:70 to 70:30, or from 40:60 to 60:40, or from 45:55 to 55:45, or about 50:50..

[0480] In embodiments, a molar ratio of a bridged phosphinimine catalyst to an unbridged phosphinimine catalyst fed to or present in a polymerization reactor is from 25:75 to 75:25.

[0481] Solution polymerization processes for the homopolymerization of ethylene or the copolymerization of ethylene with one or more than one alpha-olefin are well known in the art (see for example U.S. Pat. Nos. 6,372,864 and 6,777,509). These processes are conducted in the presence of an inert hydrocarbon solvent, typically, a C5-12 hydrocarbon which may be unsubstituted or substituted by C1-4 alkyl group such as pentane, methyl pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane and hydrogenated naphtha. An example of a suitable solvent which is commercially available is “ISOPAR®E” (Cs-12 aliphatic solvent, Exxon Chemical Co.).

[0482] In embodiments of the disclosure, the polymerization temperature in a solution phase process may be from about 80°C to about 330°C. In embodiments of the disclosure the polymerization temperature in a solution phase polymerization process is from about 80°C to about 300°C, or from about 120°C to about 330°C, or from about 120°C to about 300°C, or from about 120°C to about 280°C, or from about 120°C to about 260°C, or from about 120°C to about 250°C, or from about 120°C to about 240°C, or from about 120°C to about 230°C, or from about 120°C to about 220°C, or from about 120°C to about 210°C, or from about 120°C to about 200°C. In further embodiments, a solution phase polymerization process is carried out at a temperature of at least 140°C, or at least 160°C, or at least 170°C, or at least 180°C, or at least 190°C, or at least 200°C, or at least 210°C.

[0483] The polymerization pressure in a solution phase polymerization process may be a “medium pressure process”, meaning that the pressure in the reactor is less than about 6,000 psi (about 42,000 kiloPascals or kPa). In embodiments of the disclosure, the polymerization pressure in a solution phase polymerization process may be from about 10,000 to about 40,000 kPa, or from about 14,000 to about 22,000 kPa (i.e. from about 2,000 psi to about 3,000 psi).

[0484] Suitable monomers for copolymerization with ethylene include C3-20 alpha-olefins (including mono- and di -olefins). Some non -limiting examples of comonomers which may be copolymerized with ethylene in embodiments of the disclosure include C3-12 alphaolefins which are unsubstituted or substituted by up to two C1-6 alkyl radicals; Cs-12 vinyl aromatic monomers which are unsubstituted or substituted by up to two substituents selected from the group consisting of C1-4 alkyl radicals; and C4-12 straight chained or cyclic diolefins which are unsubstituted or substituted by a C1-4 alkyl radical. Illustrative nonlimiting examples of such alpha-olefins and which may be used in embodiments of the disclosure are one or more of propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1- decene, styrene, alpha methyl styrene, and the constrained-ring cyclic olefins such as cyclobutene, cyclopentene, dicyclopentadiene norbomene, alkyl-substituted norbomenes, alkenyl-substituted norbomenes and the like (e.g., 5-methylene-2 -norbomene, 5-ethylidene- 2 -norbomene, and bicyclo-(2,2,l)-hepta-2,5-diene).

[0485] In solution polymerization, the monomers are dissolved / dispersed in a solvent either prior to being fed to the reactor (or for gaseous monomers the monomer may be fed to a reactor so that it will dissolve in the polymerization reaction mixture). Prior to mixing, the solvent and monomers are generally purified to remove potential catalyst poisons such as water, oxygen or metal impurities. The feedstock purification may employ standard well- known practices in the art, such as for example the use of molecular sieves, alumina beds and oxygen removal catalysts, all of which are known to be useful for the purification of polymerizable monomers. The solvent itself, as well, (e.g., methyl pentane, cyclohexane, hexane or toluene) may be treated in a similar manner to remove potential catalyst poisons.

[0486] The feedstock monomers or other solution process components (e.g., solvent) may be heated or cooled prior to feeding to a solution phase polymerization reactor. In embodiments of the disclosure, the components of an active polymerization catalyst (e.g., single site catalyst molecule(s), boron-based catalyst activator(s), alkylaluminoxane(s), and a hindered phenol compound(s)) may be premixed in the solvent used for the polymerization reaction or they may be fed as separate streams to a polymerization reactor. In some embodiments, premixing may be desirable to provide a reaction time for the active polymerization catalyst components prior to entering a polymerization reaction zone (e.g., a polymerization reactor). Examples, of such an “in line mixing” technique are described in a number of patents, such as U.S. Pat. No. 5,589,555.

[0487] In an embodiment of the disclosure, a solution phase polymerization process is a continuous process. By the term “continuous process” it is meant that the polymerization process flows (e.g., solvent, ethylene, optional alpha-olefin comonomer, active polymerization catalyst components, etc.) are continuously fed to a polymerization zone (e.g., a polymerization reactor) where a polymer (e.g., ethylene homopolymer or ethylene copolymer) is formed and from which the polymer is continuously removed via a process flow effluent steam.

[0488] In a solution phase polymerization process generally, a reactor is operated under conditions which achieve a thorough mixing of the reactants and the residence time (or alternatively, the “hold up time”) of the actively polymerizing catalyst species (e.g., the activated single site catalyst) in a reactor will depend on the design and the capacity of the reactor.

[0489] In embodiments, the residence time of an actively polymerizing catalyst species in a given reactor will be from a few seconds to about 20 minutes. In further embodiments, the residence time of an actively polymerizing catalyst species in a given reactor will be less than about 10 minutes, or less than about 5 minutes, or less than about 3 minutes.

[0490] In an embodiment of the disclosure, a solution phase polymerization process is carried out in at least two polymerization reactors.

[0491] In an embodiment of the disclosure, a solution phase polymerization process is carried out in at least two polymerization reactors configured in series with one another.

[0492] In an embodiment of the disclosure, a solution phase polymerization process is carried out in at least two continuously stirred tank reactors (“CSTRs”).

[0493] In an embodiment of the disclosure, a solution phase polymerization process is carried out in at least two sequentially arranged continuously stirred tank reactors (CSTRs) with the process flows being transferred from a first upstream CSTR reactor to a second downstream CSTR. In an embodiment of the disclosure, a solution phase polymerization process is carried out in at least three polymerization reactors.

[0494] In an embodiment of the disclosure, a solution phase polymerization process is carried out in three polymerization reactors.

[0495] In an embodiment of the disclosure, a solution phase polymerization process is carried out in at least three polymerization reactors configured in series with one another.

[0496] In an embodiment of the disclosure, a solution phase polymerization process is carried out in three polymerization reactors configured in series with one another.

[0497] In an embodiment of the disclosure, a solution phase polymerization process is carried out in at least three sequentially arranged polymerization reactors, with the process flows being transferred from the first reactor to the second reactor and from the second reactor to the third reactor.

[0498] In an embodiment of the disclosure, a solution phase polymerization process is carried out in three sequentially arranged polymerization reactors, with the process flows being transferred from the first reactor to the second reactor and from the second reactor to the third reactor.

[0499] In an embodiment of the disclosure, a solution phase polymerization process is carried out in two sequentially arranged first and second reactors, each of which is a continuously stirred tank reactor (CSTR), with the process flows being transferred from the first upstream CSTR reactor to the second downstream CSTR and a third reactor which is a tubular reactor, where the third reactor is arranged sequentially to the second reactor so that process flows are transferred from the second reactor to the third reactor.

[0500] In an embodiment a first reactor is a continuously stirred tank reactor.

[0501] In an embodiment a second reactor is a continuously stirred tank reactor.

[0502] In embodiments a third reactor is a continuously stirred tank reactor or a tubular reactor (also known as a plug flow reactor).

[0503] In an embodiment a third reactor is a tubular reactor (also known as a plug flow reactor).

[0504] In an embodiment of the disclosure, a solution phase polymerization process is carried out in two sequentially arranged continuously stirred tank reactors and a tubular reactor which receives process flows from the second continuously stirred tank reactor.

[0505] In embodiments a first, second and third polymerization reactors operate at a temperature of from 80°C to 330°C. In embodiments, a first, second and third polymerization reactors operate at a pressure of from 3 MPag to 45 MPag.

[0506] In embodiments a first, second and third polymerization reactors operate at a temperature of from 80°C to 330°C and a pressure of from 3 MPag to 45 MPag.

[0507] In an embodiment, a continuous solution phase polymerization process comprises a first stirred tank polymerization reactor configured in series with a second stirred tank polymerization reactor and the mean reactor temperature in the first reactor is lower than the mean reactor temperature in the second reactor.

[0508] In an embodiment, a continuous solution phase polymerization process comprises a first stirred tank polymerization reactor configured in series with a second stirred tank polymerization reactor which is in turn configured in series with a third polymerization reactor, and the mean reactor temperature in the first reactor is lower than the mean reactor temperature in the second reactor.

[0509] In an embodiment, a continuous solution phase polymerization process comprises a first stirred tank polymerization reactor configured in series with a second stirred tank polymerization reactor which is in turn configured in series with a third polymerization reactor, and the mean reactor temperature in the first reactor is lower than the mean reactor temperature in the second reactor and the mean reactor temperature in the third reactor.

[0510] In an embodiment, a continuous solution phase polymerization process comprises a first stirred tank polymerization reactor configured in series with a second stirred tank polymerization reactor which is in turn configured in series with a third polymerization reactor, and the mean reactor temperature in the first reactor is lower than the mean reactor temperature in the second reactor, and the mean reactor temperature in the second reactor is lower than the mean temperature in the third reactor.

[0511] In embodiments, a first polymerization reactor operates at a temperature which is at least 15 °C lower, or at least 20°C, or at least 25 °C lower, or at least 30°C lower, or at least 35°C lower, or at least 40°C lower, than the temperature at which a second polymerization reactor operates.

[0512] In embodiments, a first polymerization reactor operates at a temperature of from 130°C to 220°C. In further embodiments, a first polymerization reactor operates at a temperature of from 125°C to 180°C, or from 130°C to 180°C, or from 135°C to 180°C, or from 140°C to 180°C, or from 125°C to 175°C, or from 125°C to 170°C, or from 125°C to 165°C, or from 135°C to 175°C, or from 135°C to 170°C, or from 140°C to 175°C, or from 140°C to 170°C, or from 135°C to 165°C, or from 140°C to 180°C, or from 145°C to 175°C, or from 145°C to 170°C, or from 150°C to 180°C, or from 150°C to 175°C, or from 150°C to 170°C, or from 155°C to 170°C, or from 160°C to 170°C.

[0513] In embodiments, a second polymerization reactor operates at a temperature of from 160°C to 220°C. In further embodiments, a second polymerization reactor operates at a temperature of from 165°C to 210°C, or from 165°C to 205°C, or from 165°C to 200°C, or from 170°C to 210°C, or from 170°C to 205°C, or from 170°C to 200°C, or from 175°C to 210°C, or from 175°C to 205°C, or from 175°C to 200°C, or from 180°C to 210°C, or from 180°C to 205°C, or from 180°C to 200°C, or from 185°C to 210°C, or from 185°C to 205°C, or from 185°C to 200°C, or from 190°C to 210°C, or from 190°C to 205°C, or from 190°C to 200°C.

[0514] In embodiments, a third polymerization reactor operates at a temperature of from 160°C to 240°C. In further embodiments, a third polymerization reactor operates at a temperature of froml65°C to 230°C, 165°C to 220°C, 165°C to 210°C, or from 165°C to 205°C, or from 165°C to 200°C, or from 170°C to 240°C, or from 170°C to 230°C, or from 170°C to 220°C, or from 170°C to 210°C, or from 170°C to 205°C, or from 170°C to 200°C, or from 175°C to 240°C, or from 175°C to 230°C, or from 175°C to 220°C, or from 175°C to 210°C, or from 175°C to 205°C, or from 175°C to 200°C, or from 180°C to 240°C, or from 180°C to 230°C, or from 180°C to 220°C, or from 180°C to 210°C, or from 180°C to 205°C, or from 180°C to 200°C, or from 185°C to 210°C, or from 185°C to 205°C, or from 185°C to 200°C, or from 190°C to 240°C, or from 190°C to 230°C, or from 190°C to 220°C, or from 190°C to 210°C, or from 190°C to 205°C, or from 190°C to 200°C. In still further embodiments, a third polymerization reactor operates at a temperature of at least 195°C, or at least 200°C, or at least 205°C, or at least 210°C or at least 215°C, or at least 220°C, or at least 225°C, or at least 230°C.

[0515] The term “tubular reactor” is meant to convey its conventional meaning: namely a simple tube, which unlike a CSTR is generally not agitated using an impeller, stirrer or the like. In embodiments, a tubular reactor will have a length / diameter (L / D) ratio of at least 10 / 1. In embodiments, a tubular reactor is operated adiabatically. By way of a general nonlimiting description and without wishing to be bound by theory, in a tubular reactor, as a polymerization reaction progresses, the monomer (e.g., ethylene) and / or comonomer (e.g., alpha-olefin) is increasingly consumed and the temperature of the solution increases along the length of the tube (which may improve the efficiency of separating the unreacted comonomer from the polymer solution). In embodiments, the temperature increase along the length of a tubular reactor may be greater than about 3°C. In embodiments, a tubular reactor is located downstream of a CSTR, and the discharge temperature from the tubular reactor may be at least about 3°C greater than the discharge temperature from the CSTR (and from which process flows are fed to the tubular reactor).

[0516] In embodiments, a tubular reactor may have feed ports for the addition of additional polymerization catalyst system components such as single site pre-polymerization catalysts, Zielger-Natta catalyst components, catalyst activators, cocatalysts, and hindered phenol compounds, or for the addition of monomer, comonomer, hydrogen, etc. In an alternative embodiment, no additional polymerization catalyst components are added to a tubular reactor.

[0517] In an embodiment, the total volume of a tubular reactor used in combination with at least one CSTR is at least about 10 volume percent (vol%) of the volume of at the least one CSTR, or from about 30 vol% to about 200 vol% of the at least one CSTR (for clarity, if the volume of the at least one CSTR is 1,000 liters, then the volume of the tubular reactor is at least about 100 liters, or from about 300 to 2,000 liters).

[0518] As discussed above, the temperature within a tubular reactor may increase along its length. The maximum temperature difference between the inlet and outlet of a tubular reactor may in some embodiments of the disclosure be about 100°C, or about 60°C, or about 40°C. The minimum temperature difference between the inlet and outlet of a tubular reactor may in some embodiments be about 0°C, or about 3°C, or about 10°C.

[0519] In embodiments, a tubular reactor is operated in an adiabatic fashion or it is heated.

[0520] In embodiments, on leaving the reactor system, non-reactive components may be removed (and optionally recovered) and the resulting polymer (e.g. the polyethylene composition) may be finished in a conventional manner (e.g. using a devolatilization process). In an embodiment, a two-stage devolatilization process may be employed to recover a polymer composition from a polymerization process solvent.

[0521] In embodiments of the disclosure, the pressure in the solution polymerization reactors should be high enough to maintain the polymerization solution as a single phase solution and to provide the upstream pressure to force the polymer solution from the reactors through a heat exchanger and on to polymer recovery operations. In this regard, and in embodiments of the disclosure, the operating pressure of the solution polymerization reactors can vary over a wide range. For example, the upper limit on reactor pressure in some cases may be about 45 MPag, in other cases about 30 MPag and in still other cases about 20 MPag; and the lower limit in some cases may be about 3 MPag, in other some cases about 5 MPag and in still other cases about 7 MPag. In an embodiment of the disclosure, one or more of the solution polymerization reactors can be operated at a pressure which is low enough for the one phase polymer solution to phase separate into a two phase liquid / liquid polymer solution.

[0522] The polyethylene composition product produced in a continuous solution polymerization process may be recovered using conventional devolatilization systems that are well known to persons skilled in the art, non-limiting examples include flash devolatilization systems and devolatilizing extruders.

[0523] In various embodiments, downstream of a polymerization reactor, a catalyst deactivator may be added (optionally via catalyst deactivator tank) forming a deactivated stream which is then fed (optionally via a pressure let down device) to a devolatilization system. The devolatilization system may in embodiments comprise one or more than one vapour / liquid separator or alternatively a liquid / liquid separator and one or more than one heat exchanger, and one or more than one pressure let-down device.

[0524] In embodiments, two streams are formed in V / L separator (or alternatively a liquid / liquid separator); a bottom stream containing a polyethylene composition rich solution and gaseous overhead stream. Optionally, a bottom stream enters second V / L separator (or alternatively a liquid / liquid separator and two streams are formed; bottom stream and gaseous overhead stream. Optionally, a bottom stream enters a third V / L separator (or alternatively a liquid / liquid separator) and two streams are formed; a product stream and gaseous overhead stream.

[0525] In embodiments and the product stream proceeds to polymer recovery while gaseous overhead streams are sent to a distillation column where solvent, ethylene and optional a- olefin are separated and recycled to the solution polymerization process.

[0526] The Polyethylene Composition (Made in a Single Polymerization Reactor with the Mixed Polymerization Catalyst System)

[0527] The polyethylene composition made in a single polymerization reactor according to the present disclosure may be an ethylene homopolymer or it may be an ethylene copolymer. An ethylene homopolymer is made when the polymerization of ethylene is carried in the absence of one or than one alpha-olefin, typically when one or more than one alpha-olefin is not deliberately added to a polymerization reactor. An ethylene copolymer arises, when, in addition to ethylene, one or more than one alpha-olefin is also present during the polymerization reactor, typically as a result of the deliberate addition of one or more than one alpha-olefin to a polymerization reactor. The short chain branching present in a polyethylene composition (i.e. the short chain branching per thousand backbone carbon atoms, SCB / lOOOCs) is the branching due to the presence of an a-olefin comonomer in the polyethylene composition and will for example have two carbon atoms for a 1 -butene comonomer, or four carbon atoms for a 1 -hexene comonomer, or six carbon atoms for a 1- octene comonomer, etc.

[0528] In an embodiment, the polyethylene composition made in a single polymerization reactor according to the present disclosure is an ethylene copolymer.

[0529] In embodiments, the polyethylene composition made in a single polymerization reactor according to the present disclosure is an ethylene copolymer of ethylene and one or more than one alpha-olefin selected from 1 -butene, 1 -hexene, 1 -octene or mixtures thereof.

[0530] In an embodiment, the polyethylene composition made in a single polymerization reactor according to the present disclosure is an ethylene copolymer of ethylene and 1 -octene.

[0531] In an embodiment, the polyethylene composition made in a single polymerization reactor will comprise a first polyethylene component made by a bridged phosphinimine catalyst and a second polyethylene component made by an unbridged phosphinimine catalyst.

[0532] In an embodiment, the polyethylene composition made in a single polymerization reactor will comprise a relatively higher molecular weight (where molecular weight may be defined by, for example, Mn, Mw, or Mz) polyethylene component made by a bridged phosphinimine catalyst and a relatively lower molecular weight polyethylene component made by an unbridged phosphinimine catalyst.

[0533] In an embodiment, the polyethylene composition made in a single polymerization reactor will comprise a relatively higher molecular weight (where molecular weight may be defined by, for example, Mn, Mw, or Mz) polyethylene component made by an unbridged phosphinimine catalyst and a relatively lower molecular weight polyethylene component made by a bridged phosphinimine catalyst.

[0534] In an embodiment, the polyethylene composition made in a single polymerization reactor will comprise a polyethylene component made by a bridged phosphinimine catalyst and a polyethylene component made by an unbridged phosphinimine catalyst and the polyethylene component made by the bridged phosphinimine catalyst has a higher molecular weight (where molecular weight may be defined by, for example, Mn, Mw, or Mz) than the polyethylene component made by the unbridged phosphinimine catalyst. In an embodiment, the polyethylene composition made in a single polymerization reactor will comprise a polyethylene component made by a bridged phosphinimine catalyst and a polyethylene component made by an unbridged phosphinimine catalyst and the polyethylene component made by the bridged phosphinimine catalyst has a lower molecular weight (where molecular weight may be defined by, for example, Mn, Mw, or Mz) than the polyethylene component made by the unbridged phosphinimine catalyst.

[0535] In an embodiment, the polyethylene composition made in a single polymerization reactor will comprise a relatively lower density polyethylene component made by a bridged phosphinimine catalyst and a relatively higher density polyethylene component made by an unbridged phosphinimine catalyst.

[0536] In an embodiment, the polyethylene composition made in a single polymerization reactor will comprise a relatively lower density polyethylene component made by an unbridged phosphinimine catalyst and a relatively higher density polyethylene component made by a bridged phosphinimine catalyst.

[0537] In an embodiment, the polyethylene composition made in a single polymerization reactor will comprise a polyethylene component made by a bridged phosphinimine catalyst and a polyethylene component made by an unbridged phosphinimine catalyst and the polyethylene component made by the bridged phosphinimine catalyst has a lower density than polyethylene component made by the unbridged phosphinimine catalyst.

[0538] In an embodiment, the polyethylene composition made in a single polymerization reactor will comprise a polyethylene component made by a bridged phosphinimine catalyst and a polyethylene component made by an unbridged phosphinimine catalyst and the polyethylene component made by the bridged phosphinimine catalyst has a higher density than polyethylene component made by the unbridged phosphinimine catalyst.

[0539] In an embodiment, the polyethylene composition made in a single polymerization reactor will comprise a polyethylene component made by a bridged phosphinimine catalyst and a polyethylene component made by an unbridged phosphinimine catalyst and the polyethylene component made by the bridged phosphinimine catalyst has a higher amount of short chain branching per thousand carbon atoms (SCB / lOOOCs) than polyethylene component made by the unbridged phosphinimine catalyst.

[0540] In an embodiment, the polyethylene composition made in a single polymerization reactor will comprise a polyethylene component made by a bridged phosphinimine catalyst and a polyethylene component made by an unbridged phosphinimine catalyst and the polyethylene component made by the bridged phosphinimine catalyst has a higher amount of short chain branching per thousand carbon atoms (SCB / lOOOCs) and a higher molecular weight (where molecular weight may be defined by, for example, Mn, Mw, or Mz) than polyethylene component made by the unbridged phosphinimine catalyst.

[0541] In an embodiment, the polyethylene composition made in a single polymerization reactor will comprise a polyethylene component made by a bridged phosphinimine catalyst and a polyethylene component made by an unbridged phosphinimine catalyst and the polyethylene component made by the bridged phosphinimine catalyst has a higher amount of short chain branching per thousand carbon atoms (SCB / lOOOCs), a higher molecular weight (where molecular weight may be defined by, for example, Mn, Mw, or Mz) and a lower density than polyethylene component made by the unbridged phosphinimine catalyst.

[0542] In an embodiment, the polyethylene composition made in a single polymerization reactor has a bimodal profile in a gel permeation chromatography profile generated according to the method of ASTM D6474-99, wherein the bimodal profile comprises a first elution peak and a second elution peak.

[0543] In an embodiment, the polyethylene composition made in a single polymerization reactor has an elution profile generated by temperature rising elution fractionation (TREF) analysis comprising a first elution peak and a second elution peak, wherein the first and second elution peaks are separated by at least 3 °C.

[0544] In further embodiments, the polyethylene composition made in a single polymerization reactor has an elution profile generated by temperature rising elution fractionation (TREF) analysis comprising a first elution peak and a second elution peak, wherein the first and second elution peaks are separated by at least at least 5°C, or at least 7°C, or at least 10°C, or at least 12°C, or at least I5°C, or at least 17°C or at least 20°C.

[0545] In an embodiment of the disclosure, the polyethylene composition made in a single polymerization reactor has a reversed or partially reversed comonomer distribution profile by gel permeation chromatography (GPC) with Fourier Transform Infra-Red (FTIR) detection.

[0546] If the comonomer incorporation decreases with molecular weight, as measured using GPC-FTIR, the distribution is described as “normal”. If the comonomer incorporation is approximately constant with molecular weight, as measured using GPC-FTIR, the comonomer distribution is described as “flat” or “uniform”. The terms “reversed comonomer distribution” and “partially reversed comonomer distribution” mean that in the GPC-FTIR data obtained for the polyethylene composition, there is one or more higher molecular weight components having a higher comonomer incorporation than in one or more lower molecular weight components. The term “reversed comonomer distribution” is used herein to mean, that across the molecular weight range of the polyethylene composition, comonomer contents for the various polymer fractions are not substantially uniform and the higher molecular weight fractions thereof have proportionally higher comonomer contents (i.e. if the comonomer incorporation rises with molecular weight, the distribution is described as “reverse” or “reversed”). Where the comonomer incorporation rises with increasing molecular weight and then declines, the comonomer distribution is still considered “reversed”, but may also be described as “partially reversed”.

[0547] In an embodiment, the polyethylene composition made in a single polymerization reactor has a reversed comonomer distribution as determined by gel permeation chromatography (GPC) with Fourier Transform Infra-Red (FTIR) detection.

[0548] In an embodiment, the polyethylene composition made in a single polymerization reactor has a partially reversed comonomer distribution as determined by gel permeation chromatography (GPC) with Fourier Transform Infra-Red (FTIR) detection.

[0549] In an embodiment of the disclosure, the polyethylene composition made in a single polymerization reactor has a “partially reversed” comonomer distribution and shows a peak or a maximum in the comonomer distribution profile as determined by gel permeation chromatography (GPC) with Fourier Transform Infra-Red (FTIR) detection.

[0550] The following examples are presented for the purpose of illustrating selected embodiments of this disclosure; it being understood, that the examples presented do not limit the claims presented.

[0551] EXAMPLES

[0552] Prior to testing, each specimen was conditioned for at least 24 hours at 23 ±2°C and 50 ±10% relative humidity and subsequent testing was conducted at 23 ±2°C and 50 ±10% relative humidity. Herein, the term “ASTM conditions” refers to a laboratory that is maintained at 23 ±2°C and 50 ±10% relative humidity; and specimens to be tested were conditioned for at least 24 hours in this laboratory prior to testing. ASTM refers to the American Society for Testing and Materials.

[0553] Polyethylene composition densities were determined using ASTM D792-13 (November 1, 2013).

[0554] Melt Index

[0555] The polyethylene composition melt index was determined using ASTM D1238 (August 1, 2013). Melt indexes, h, L, ho and hi were measured at 190°C, using weights of 2.16 kg, 6.48 kg, 10 kg and a 21.6 kg respectively. Herein, the term “stress exponent” or its acronym “S.Ex.”, is defined by the following relationship:

[0556] S.Ex.= log (l6 / h) / log(6480 / 2160) wherein L and h are the melt flow rates measured at 190°C using 6.48 kg and 2. 16 kg loads, respectively. In this disclosure, melt index was expressed using the units of g / 10 minutes or g / 10 min or dg / minutes or dg / min; these units are equivalent.

[0557] Gel Permeation Chromatography (GPC)

[0558] Polyethylene composition molecular weights, Mn, Mwand Mz(in g / mol) as well the as the polydispersity (Mw / Mn), were determined using ASTM D6474-12 (Dec. 15, 2012). Polymer sample solutions (1 to 2 mg / mL) were prepared by heating the polymer in 1,2,4- trichlorobenzene (TCB) and rotating on a wheel for 4 hours at 150°C in an oven. The antioxidant 2,6-di-tert-butyl-4-methylphenol (BHT) was added to the mixture in order to stabilize the polymer against oxidative degradation. The BHT concentration was 250 ppm. Sample solutions were chromatographed at 140°C on a PL 220 high-temperature chromatography unit equipped with four SHODEX columns (HT803, HT804, HT805 and HT806) using TCB as the mobile phase with a flow rate of 1.0 mL / minute, with a differential refractive index (DRI) as the concentration detector. BHT was added to the mobile phase at a concentration of 250 ppm to protect GPC columns from oxidative degradation. The sample injection volume was 200 pL. The GPC raw data were processed with the CIRRUS GPC software. The GPC columns were calibrated with narrow distribution polystyrene standards. The polystyrene molecular weights were converted to polyethylene molecular weights using the Mark-Houwink equation, as described in ASTM D6474-12 (Dec. 15, 2012).

[0559] GPC-FTIR

[0560] Polyethylene composition (polymer) solutions (2 to 4 mg / mL) were prepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) and rotating on a wheel for 4 hours at 150°C in an oven. The antioxidant 2,6-di-tert-butyl-4-methylphenol (BHT) was added to the mixture in order to stabilize the polymer against oxidative degradation. The BHT concentration was 250 ppm. Sample solutions were chromatographed at 140°C on a Waters GPC 150C chromatography unit equipped with four SHODEX columns (HT803, HT804, HT805 and HT806) using TCB as the mobile phase with a flow rate of 1.0 mL / minute, with a FTIR spectrometer and a heated FTIR flow through cell coupled with the chromatography unit through a heated transfer line as the detection system. BHT was added to the mobile phase at a concentration of 250 ppm to protect SEC columns from oxidative degradation. The sample injection volume was 300 pL. The raw FTIR spectra were processed with OPUS FTIR software and the polymer concentration and methyl content were calculated in real time with the Chemometric Software (PLS technique) associated with the OPUS. Then the polymer concentration and methyl content were acquired and baseline-corrected with the CIRRUS GPC software. The SEC columns were calibrated with narrow distribution polystyrene standards. The polystyrene molecular weights were converted to polyethylene molecular weights using the Mark-Houwink equation, as described in the ASTM standard test method D6474. The comonomer content was calculated based on the polymer concentration and methyl content predicted by the PLS technique as described in Paul J. DesLauriers, Polymer 43, pages 159-170 (2002); herein incorporated by reference.

[0561] The GPC-FTIR method measures total methyl content, which includes the methyl groups located at the ends of each macromolecular chain, i.e. methyl end groups. Thus, the raw GPC-FTIR data must be corrected by subtracting the contribution from methyl end groups. To be more clear, the raw GPC-FTIR data overestimates the amount of short chain branching (SCB) and this overestimation increases as molecular weight (M) decreases. In this disclosure, raw GPC-FTIR data was corrected using the 2-methyl correction. At a given molecular weight (M), the number of methyl end groups (NE) was calculated using the following equation: NE = 28000 / M, and NE (M dependent) was subtracted from the raw GPC-FTIR data to produce the SCB / 1000C (2 -Methyl Corrected) GPC-FTIR data. Unsaturation Content

[0562] The quantity of unsaturated groups, i.e., double bonds, in a polyethylene composition was determined according to ASTM D3124-98 (vinylidene unsaturation, published March 2011) and ASTM D6248-98 (vinyl and trans unsaturation, published July 2012). A polymer sample was: a) first subjected to a carbon disulfide extraction to remove additives that may interfere with the analysis; b) the sample (pellet, film or granular form) was pressed into a plaque of uniform thickness (0.5 mm); and c) the plaque was analyzed by FTIR.

[0563] CTREF

[0564] The “Composition Distribution Branching Index” or “CDBI” or an elution profile of a polyethylene composition can be determined using a crystal-TREF unit (a “CTREF” unit) commercially available form Polymer Char (Valencia, Spain). The acronym “TREF” refers to Temperature Rising Elution Fractionation. A sample of polyethylene composition (80 to 100 mg) was placed in the reactor of the Polymer Char crystal-TREF unit, the reactor was filled with 35 ml of 1,2,4-trichlorobenzene (TCB), heated to 150°C and held at this temperature for 2 hours to dissolve the sample. An aliquot of the TCB solution (1.5 mb) was then loaded into the Polymer Char TREF column filled with stainless steel beads and the column was equilibrated for 45 minutes at 110°C. The polyethylene composition was then crystallized from the TCB solution, in the TREF column, by slowly cooling the column from 110°C to 30°C using a cooling rate of 0.09°C per minute. The TREF column was then equilibrated at 30°C for 30 minutes. The crystallized polyethylene composition was then eluted from the TREF column by passing pure TCB solvent through the column at a flow rate of 0.75 mL / minute as the temperature of the column was slowly increased from 30°C to 120°C using a heating rate of 0.25°C per minute. At the end of each sample run, the CTREF column was cleaned for 30 minutes; specifically, with the CTREF column temperature at or above the dissolution temperature (e.g. 160°C), TCB flowed (0.5 mL / minute) through the column for 30 minutes. Using Polymer ChAR software, an Excel spreadsheet and CTREF software developed in-house, a TREF distribution curve was generated as the polyethylene composition was eluted from the TREF column, i.e., a TREF distribution curve is a plot of the quantity (or intensity) of polymeric material eluting from the column as a function of TREF elution temperature. Those skilled in the art will understand that a calibration curve is required to convert a CTREF elution temperature to comonomer content, i.e. the amount of comonomer in the ethylene / a-olefin polymer fraction that elutes at a specific temperature. The generation of such calibration curves are described in the prior art, e.g. Wild, et al., J. Polym. Sci., Part B, Polym. Phys., Vol. 20 (3), pages 441-455. A CDBIso may be calculated from the TREF distribution curve for each polyethylene composition analyzed. The “CDBIso” is defined as the percent of polymer whose composition is within 50% of the median comonomer composition (50% on each side of the median comonomer composition); this definition is consistent with that described in WO 93 / 03093 and United States Patent 5,376,439; it is calculated from the CTREF composition distribution curve and the normalized cumulative integral of the CTREF composition distribution curve. The CTREF procedures described above are also used to determine the modality of a CTREF profile, the temperatures or temperatures ranges where elution intensity maxima (elution peaks) occur, and if desirable the weight percent (wt%) of polyethylene composition components or fractions which elute over a selected temperature range. Solution Phase Polymerization: Continuous Ethylene / 1 -Octene Copolymerization

[0565] A continuous solution phase polymerizations unit (CPU) was used to assess the use of two different single site catalysts in a single continuous solution phase polymerization reactor. Specifically, different amounts of a bridged phosphinimine catalyst and an unbridged phosphinimine catalyst, having the structures A and B respectively (shown below), were fed to a CPU along with catalyst activator components and a hindered phenol.

[0566] The continuous solution phase polymerizations were conducted in a continuously stirred, 71.5 mE reactor unit using cyclohexane as the process solvent. The reactor was operated at 190°C. An upstream mixing reactor having a 20 mE volume was operated at 5°C lower than the polymerization reactor. The mixing reactor was used to pre-heat the ethylene (“C2” in the Tables 1 and 2), 1-octene (“1-C8” in the Tables 1 and 2) and make-up solvent streams. Catalyst feeds (ort / io-xylene or cyclohexane solutions of the bridged phopshinimine catalyst (A), the unbridged phosphinimine catalyst (B), the boron-based catalyst activator, (Ph3C)[B(C6Fs)4] (“trityl borate”), an aluminum based co-catalyst (modified methylaluminoxane, “MMAO-7”), a hindered phenol (2,6-di-tert-butyl-4- ethylphenol, “BHEB”), and additional cyclohexane solvent flow were added directly to the polymerization reactor in a continuous process or combined as described below. The aluminum co-catalyst solution was either added directly to the polymerization reactor or was combined in-line with the solution of the bridged phosphinimine catalyst or unbridged phosphinimine catalyst prior to injection into the polymerization reactor. In cases where a hindered phenol, BHEB, was used, solutions of MMAO-7 and BHEB were combined upstream of the reactor or upstream of the mixing point with the solution of bridged phosphinimine catalyst or unbridged phosphinimine catalyst. The solution of boron-based catalyst activator was either added directly to the reactor or combined with a solution of bridged phosphinimine catalyst or unbridged phosphinimine catalyst immediately before combining with the solution of aluminum co-catalyst. A total continuous flow of 27 mL / min into the polymerization reactor was maintained. The B / Ti molar ratio was between 0.9 and 1.5. The Al / Ti molar ratio between about 18 and 32. The BHEB / A1 molar ratio was maintained at around 0.3.

[0567] Ethylene / 1 -octene copolymers were made at a 1 -octene / ethylene weight ratio of 0.30. The ethylene was fed at a rate of 3.0 g / min. The CPU system operated at a pressure of 10.5 MPa. The solvent, monomer, and comonomer streams were all purified by purification trains before being fed to the reactor. The polymerization activity, kp(expressed in mM^-min'1), is defined as: where Q is ethylene conversion (%) (measured using an online a near infra-red, NIR detector), [Ti] is catalyst concentration in the reactor (pM), and HUT is hold-up time in the reactor (2.6 min). Copolymer samples were collected at 90±l % ethylene conversion (Q) unless otherwise stated, dried in a vacuum oven, and then ground and homogenized prior to analysis. General copolymerization conditions are listed in Table 1.

[0568] TABLE 1

[0569] CPU Polymerization Run Conditions Using a Mixed Single Site Catalyst

[0570] (Catalyst A / Catalyst B)

[0571] The GPC-FTIR analysis of the polyethylene compositions made during the CPU polymerization runs 1 to 8 are shown in Figure 1. The GPC analysis of the polyethylene compositions made during the CPU polymerization runs 1 to 8 are shown in Figure 2. The CTREF analysis of the polyethylene compositions made during the CPU polymerization runs 1 to 8 are shown in Figure 3. The corresponding weight percent of polymer material eluting in a TREF analysis at a temperature of below 82°C is shown plotted against the mol ratio of bridged phosphinimine catalyst to unbridged phosphinimine catalyst used in the reactor during polymerization runs 1 to 8 is shown Figure 4.

[0572] The data presented in Figures 1 and 2, shows that as the amount of bridged phosphinimine catalyst, A is increased relative to the amount of unbridged phosphinimine catalyst, B, the amount of a polyethylene component having a relatively higher molecular weight increase. This is consistent with the bridged phosphinimine catalyst, A, polymerizing ethylene and an alpha-olefin to higher molecular weights than the unbridged phosphinimine catalyst, B, under similar polymerization conditions. Also, evidenced from the data in Figure 1, is that as the amount of bridged phosphinimine catalyst, A is increased relative to the amount of unbridged phosphinimine catalyst, B, the amount of short chain branching occurring at higher relative molecular weights is also increased. Or to put it another way, the distribution of short chain branching, which is the result of 1 -octene uptake into the polymer composition becomes more reversed (the slope of the short chain branching content becomes more positive with respect to increasing molecular weight). This is consistent with the bridged phosphinimine catalyst, A, incorporating larger amounts of 1 -octene when copolymerized with ethylene than the unbridged phosphinimine catalyst, B, under similar polymerization conditions.

[0573] From Figures 1, 2 and 3, a person skilled in the art, will see that due to the different relative molecular weight performances of the bridged phosphinimine catalyst, A and the unbridged phosphinimine catalyst, B, a distinctly bimodal GPC profile is observed, when the relative amounts of a first polyethylene component made by the bridged phosphinimine catalyst, A, and a second polyethylene component made by the unbridged phosphinimine catalyst, B are both present in significant amounts. Similarly, the relatively divergent abilities, of the bridged phosphinimine catalyst, A, and the unbridged phosphinimine catalyst, B to incorporate an alpha-olefin, allows for polyethylene compositions which have highly reversed comonomer incorporation (such that the short chain branching per 1000 carbon backbone atoms increases as weight average molecular weight increases) to be made in a single polymerization reactor.

[0574] The above results contrasted those of mixed catalysts systems where two different, but unbridged phosphinimine catalysts were used. A continuous solution phase polymerizations unit (CPU) was used to assess the use of two different single site catalysts in a single continuous solution phase polymerization reactor. Specifically, different amounts of unbridged phosphinimine catalysts having the structures B and C respectively (shown below), were fed to a CPU along with catalyst activator components and a hindered phenol.

[0575] The continuous solution phase polymerizations were conducted in a continuously stirred, 71.5 mL reactor unit using cyclohexane as the process solvent. The reactor was operated at 190°C. An upstream mixing reactor having a 20 mL volume was operated at 5°C lower than the polymerization reactor. The mixing reactor was used to pre-heat the ethylene, 1-octene and make-up solvent streams. Catalyst feeds (o / v / io-xylcnc or cyclohexane solutions of the metallocene catalyst, the phosphinimine catalyst, the boron- based catalyst activator, (Ph3C)[B(C6Fs)4] (“trityl borate”), an aluminum based co-catalyst (modified methylaluminoxane, “MMAO-7”), a hindered phenol (2,6-di-tert-butyl-4- ethylphenol, “BHEB”), and additional cyclohexane solvent flow were added directly to the polymerization reactor in a continuous process or combined as described below. The aluminum co-catalyst solution was either added directly to the polymerization reactor or was combined in-line with the solution of the unbridged phosphinimine catalyst prior to injection into the polymerization reactor. In cases where a hindered phenol, BHEB, was used, solutions of MMAO-7 and BHEB were combined upstream of the reactor or upstream of the mixing point with the solution of unbridged phosphinimine catalyst. The solution of boron-based catalyst activator was either added directly to the reactor or combined with a solution of unbridged phosphinimine catalyst immediately before combining with the solution of aluminum co-catalyst. A total continuous flow of 27 mL / min into the polymerization reactor was maintained. The B / Ti molar ratio was 1.2 as stated in the table. The Al / Ti molar ratio between about 18 and 32 as stated in the table. The BHEB / A1 molar ratio was maintained at around 0.3.

[0576] Ethylene / 1-octene copolymers were made at a 1-octene / ethylene weight ratio of 1.0. The ethylene was fed at a rate of 3.5 g / min. The CPU system operated at a pressure of 10.5 MPa. The solvent, monomer, and comonomer streams were all purified by purification trains before being fed to the reactor. The polymerization activity, kp(expressed in mM" hmin'1), is defined as: where Q is ethylene conversion (%) (measured using gas chromatography), [Ti] is catalyst concentration in the reactor (pM), and HUT is hold-up time in the reactor (2.6 min).

[0577] Copolymer samples were collected at 90±l % ethylene conversion (Q) unless otherwise stated, dried in a vacuum oven, and then ground and homogenized prior to analysis.

[0578] General copolymerization conditions are listed in Table 2.

[0579] TABUE 2

[0580] CPU Polymerization Run Conditions Using a Mixed Single Site Catalyst

[0581] (Catalyst B / Catalvst C)

[0582] The GPC-FTIR analysis of the polyethylene compositions made during the CPU polymerization runs 9 to 13 are shown in Figure 5. The GPC analysis of the polyethylene compositions made during the CPU polymerization runs 9 to 13 are shown in Figure 6. The temperature rising elution fractionation analyses carried out substantially as described above (under the heading CTREF) of the polyethylene compositions made during the CPU polymerization runs 9 to 13 are shown in Figure 7.

[0583] The data in Figures 5 and 6 shows that when unbridged phosphinimine catalyst B, is used in combined with unbridged phosphinimine catalyst, C, using the polymerization conditions shown in Table 2, neither a distinctly bimodal polyethylene composition in the GPC, nor one having a highly reversed comonomer content in the GPC-FTIR was achieved.

[0584] Non-limiting embodiments of the present disclosure include the following: Embodiment 1. A solution phase polymerization process to make a polyethylene composition, the process comprising: feeding ethylene, a process solvent, a bridged phosphinimine catalyst, an unbridged phosphinimine catalyst, one or more than one catalyst activator, optionally one or more than one a-olefin and optionally hydrogen to a polymerization reactor to produce the polyethylene composition, wherein the polyethylene composition comprises a first polyethylene component which is made by the bridged phosphinimine catalyst and a second polyethylene component which is made by the unbridged phosphinimine catalyst.

[0585] Embodiment 2. The process of Embodiment 1 wherein the first polyethylene component has a weight average molecular weight, Mw1, the second polyethylene component has a weight average molecular weight, Mw2, and wherein Mw1is greater than Mw2.

[0586] Embodiment 3. The process of Embodiment 1 or 2 wherein when one or more than one a-olefin is fed to the polymerization reactor, the first polyethylene component has a number of short chain branches per thousand backbone carbon atoms, SCB1, the second polyethylene component has a number of short chain branches per thousand backbone carbon atoms, SCB2, and wherein SCB1is greater than SCB2.

[0587] Embodiment 4. The process of Embodiment 1 or 2 wherein when one or more than one a-olefin is fed to the polymerization reactor the polyethylene composition has a reversed comonomer distribution as determined by gel permeation chromatography (GPC) with Fourier Transform Infra-Red (FTIR) detection.

[0588] Embodiment 5. The process of Embodiment 1, 2, 3, or 4 wherein the first polyethylene component has a density, d1, the second polyethylene component has a density, d2, and wherein d1is less than d2.

[0589] Embodiment 6. The process of Embodiment 1, 2, 3, 4, or 5 wherein the polyethylene composition has a bimodal profile in a gel permeation chromatography profile generated according to the method of ASTM D6474-99, wherein the bimodal profile comprises a first elution peak and a second elution peak.

[0590] Embodiment 7. The process of any one of Embodiments 1 to 6 wherein when one or more than one a-olefin is fed to the polymerization reactor the polyethylene composition has an elution profile generated by temperature rising elution fractionation (TREF) analysis comprising a first elution peak and a second elution peak, wherein the first and second elution peaks are separated by at least 3°C. Embodiment 8. The process of any one of Embodiments 1 to 7 wherein the polymerization reactor is operated at a temperature of from 80°C to 330°C.

[0591] Embodiment 9. The process of any one of Embodiments 1 to 8 wherein the polymerization reactor is operated at a pressure of from 3 MPag to 45 MPag.

[0592] Embodiment 10. The process of any one of Embodiments 1 to 9 wherein the polymerization reactor is a continuously stirred tank reactor.

[0593] Embodiment 11. The process of any one of Embodiments 1 to 10 wherein a molar ratio of the bridged phosphinimine catalyst to the unbridged phosphinimine catalyst present in the polymerization reactor is from 25:75 to 75:25.

[0594] Embodiment 12. The process of any one of Embodiments 1 to 11 wherein the bridged phosphinimine catalyst is represented by formula I: wherein

[0595] M is Ti, Zr or Hf;

[0596] R1and R2are each independently selected from the group consisting of hydrogen and Rx; or R1and R2together with the P atom to which they are attached form a 3-10 membered heterocyclic group which is unsubstituted or further substituted by one or more substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; each Rxis independently selected from the group consisting of a halogen atom; a Ci- 30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom, C1-20 alkyl group, C1-20 alkoxy group, C7-20 alkylaryl group, C7-20 arylalkyl group, C6-20 aryl group, C6-20 aryloxy group, C7-20 alkylaryloxy group, and / or C7-20 arylalkyloxy group; an amido group of the formula -NR’ 2; a silyl group of the formula -Si(Ra)3; a germanyl group of the formula -Ge(Ra)3; and a phosphinimine group of the formula -N=P(Rb)(Rc)(Rd); wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group; wherein each Rais independently selected from the group consisting of hydrogen, Ci-8 alkyl group, Ci-8 alkoxy group, Ce-20 aryloxy group and Ce-20 aryl group; and Rb, Rc, Rd, are each independently a Ci-20 alkyl group; each X1is an activatable ligand;

[0597] Cy is a cyclopentadienyl-type ligand covalently bound to L and coordinated to M via T|-bonding; and

[0598] L is a bridging group containing a contiguous chain of 2 or 3 atoms connecting P with Cy.

[0599] Embodiment 13. The process of Embodiment 12 wherein M is Ti.

[0600] Embodiment 14. The process of any one of Embodiments 1 to 13 wherein the unbridged phosphinimine catalyst is represented by formula XI: (Cyu)Mu(N=PRp3)(X1)2 (XI) wherein

[0601] Muis Ti, Zr or Hf;

[0602] Cyuis selected from the group consisting of unsubstituted cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl, substituted indenyl, unsubstituted fluorenyl and substituted fluorenyl; and

[0603] Rpare each independently selected from the group consisting of a hydrogen atom; a halogen atom; a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom, C1-20 alkyl group, C1-20 alkoxy group, C7-20 alkylaryl group, C7-20 arylalkyl group, C6-20 aryl group, C6-20 aryloxy group, C7-20 alkylaryloxy group, and / or C7-20 arylalkyloxy group; an amido group of the formula -NR’2; a silyl group of the formula -Si(Ra)3; a germanyl group of the formula -Ge(Ra)3; and a phosphinimine group of the formula -N=P(Rb)(Rc)(Rd); wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group; wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group and C6-20 aryl group; and Rb, Rc, Rd, are each independently a C1-20 alkyl group; and each X1is an activatable ligand.

[0604] Embodiment 15. The process of Embodiment 14 wherein Muis Ti.

[0605] INDUSTRIAL APPLICABILITY

[0606] Polyethylene compositions are made by feeding a bridged phosphinimine catalyst and an unbridged phosphinimine catalyst to the same polymerization reactor where ethylene is polymerized optionally together with one or more than one alpha-olefin.

Claims

CLAIMS1. A solution phase polymerization process to make a polyethylene composition, the process comprising: feeding ethylene, a process solvent, a bridged phosphinimine catalyst, an unbridged phosphinimine catalyst, one or more than one catalyst activator, optionally one or more than one a-olefin and optionally hydrogen to a polymerization reactor to produce the polyethylene composition, wherein the polyethylene composition comprises a first polyethylene component which is made by the bridged phosphinimine catalyst and a second polyethylene component which is made by the unbridged phosphinimine catalyst.

2. The process of claim 1 wherein the first polyethylene component has a weight average molecular weight, Mw1, the second polyethylene component has a weight average molecular weight, Mw2, and wherein Mw1is greater than Mw2.

3. The process of claim 1 wherein when one or more than one a-olefin is fed to the polymerization reactor, the first polyethylene component has a number of short chain branches per thousand backbone carbon atoms, SCB1, the second polyethylene component has a number of short chain branches per thousand backbone carbon atoms, SCB2, and wherein SCB1is greater than SCB2.

4. The process of claim 1 wherein when one or more than one a-olefin is fed to the polymerization reactor the polyethylene composition has a reversed comonomer distribution as determined by gel permeation chromatography (GPC) with Fourier Transform Infra-Red (FTIR) detection.

5. The process of claim 1 wherein the first polyethylene component has a density, d1, the second polyethylene component has a density, d2, and wherein d1is less than d2.

6. The process of claim 1 wherein the polyethylene composition has a bimodal profile in a gel permeation chromatography profile generated according to the method of ASTM D6474-99, wherein the bimodal profile comprises a first elution peak and a second elution peak.

7. The process of claim 1 wherein when one or more than one a-olefin is fed to the polymerization reactor the polyethylene composition has an elution profile generated by temperature rising elution fractionation (TREF) analysis comprising a first elution peak and a second elution peak, wherein the first and second elution peaks are separated by at least 3°C.

8. The process of claim 1 wherein the polymerization reactor is operated at a temperature of from 80°C to 330°C.

9. The process of claim 1 wherein the polymerization reactor is operated at a pressure of from 3 MPag to 45 MPag.

10. The process of claim 1 wherein the polymerization reactor is a continuously stirred tank reactor.

11. The process of claim 1 wherein a molar ratio of the bridged phosphinimine catalyst to the unbridged phosphinimine catalyst present in the polymerization reactor is from 25:75 to 75:25.

12. The process of claim 1 wherein the bridged phosphinimine catalyst is represented by formula I:whereinM is Ti, Zr or Hf;R1and R2are each independently selected from the group consisting of hydrogen and Rx; or R1and R2together with the P atom to which they are attached form a 3-10 membered heterocyclic group which is unsubstituted or further substituted by one or more substituent selected from the group consisting of a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C7-20 alkylaryl group, a C7-20 arylalkyl group, a C6-20 aryl group, a C6-20 aryloxy group, a C7-20 alkylaryloxy group, and a C7-20 arylalkyloxy group; each Rxis independently selected from the group consisting of a halogen atom; a Ci-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom, C1-20 alkyl group, C1-20 alkoxy group, C7-20 alkylaryl group, C7-20 arylalkyl group, C6-20 aryl group, C6-20 aryloxy group, C7-20 alkylaryloxy group, and / or C7-20 arylalkyloxy group; an amido group of the formula -NR’ 2; a silyl group of the formula -Si(Ra)3; a germanyl group of the formula -Ge(Ra)3; and a phosphinimine group of the formula -N=P(Rb)(Rc)(Rd); wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group; wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxygroup, Ce-20 aryloxy group and Ce-20 aryl group; and Rb, Rc, Rd, are each independently a Ci-20 alkyl group; each X1is an activatable ligand;Cy is a cyclopentadienyl-type ligand covalently bound to L and coordinated to M via T|-bonding; andL is a bridging group containing a contiguous chain of 2 or 3 atoms connecting P with Cy.

13. The process of claim 12 wherein M is Ti.

14. The process of claim 1 wherein the unbridged phosphinimine catalyst is represented by formula XI:(Cyu)Mu(N=PRp3)(X1)2 (XI) whereinMuis Ti, Zr or Hf;Cyuis selected from the group consisting of unsubstituted cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl, substituted indenyl, unsubstituted fluorenyl and substituted fluorenyl; andRpare each independently selected from the group consisting of a hydrogen atom; a halogen atom; a C1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom, C1-20 alkyl group, C1-20 alkoxy group, C7-20 alkylaryl group, C7-20 arylalkyl group, C6-20 aryl group, C6-20 aryloxy group, C7-20 alkylaryloxy group, and / or C7-20 arylalkyloxy group; an amido group of the formula -NR’2; a silyl group of the formula -Si(Ra)3; a germanyl group of the formula -Ge(Ra)3; and a phosphinimine group of the formula -N=P(Rb)(Rc)(Rd); wherein each R’ is independently selected from the group consisting of hydrogen, C1-20 alkyl group, and C6-20 aryl group; wherein each Rais independently selected from the group consisting of hydrogen, C1-8 alkyl group, C1-8 alkoxy group, C6-20 aryloxy group and C6-20 aryl group; and Rb, Rc, Rd, are each independently a C1-20 alkyl group; and each X1is an activatable ligand.

15. The process of claim 14 wherein Muis Ti.

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