Pyridyldiamide metal catalysts and processes to produce polyolefins

Disclosed are new classes of pyridyldiamide catalyst components useful in olefin polymerization, an example of which includes:wherein M is a hafnium or zirconium; R1 and R11 are selected from phenyl and substituted phenyl, wherein the substitutions are selected from C1 to C5 hydrocarbyls, preferably C2 to C4 hydrocarbyls, and can reside in any of the ortho, meta, para positions on the phenyl ring; R2′ and R2″ are selected independently from hydrogen and C1 to C6 hydrocarbyls, preferably hydrogen; R10 is a hydrocarbyl bridging group; R3, R4, and R5 are independently selected from hydrogen, hydrocarbyls, and substituted hydrocarbyls; and R6, R7, R8, and R9 are independently selected from hydrogen, hydrocarbyls, and substituted hydrocarbyls; wherein R6 and R7 form an aromatic ring or R7 is hydrogen and R6 is selected from methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, and tert-butyl, preferably methyl.

FIELD OF THE INVENTION

This invention relates to classes of pyridyldiamide metal catalysts components and their use in the polymerization of ethylene and/or propylene.

BACKGROUND OF THE INVENTION

Though single-site polymerization catalysts for polyolefin polymerization are well known, there is still a desire for higher activity catalysts capable of operating at high temperatures, and capable of producing crystalline polymers with specific melting points and degrees of crystallinity. There is also a need to understand how to tailor such catalysts such that the polymers produced from these catalysts can be fine-tuned to meet a variety of commercial needs. It would be desirable to utilize the same class of compounds within a given class of catalyst compounds that have similar reactor behavior so that different products can be produced without major disruption in the overall commercial production of polymer.

WO 2007/130306 and WO 2007/130242 disclose transition metal imidazoldiyl olefin polymerization catalysts that are distinct from the present invention. U.S. Pat. No. 6,953,764 discloses pyridyl amide catalysts for olefin polymerization that are distinct from the present invention. Pyridyldiamide catalysts have been described in U.S. Pat. No. 7,973,116; US 2011/0224391; US 2011/0301310; and US 2012/0071616. These pyridyldiamide catalysts are useful in making polyolefins.

The inventors here have found a class of pyridyldiamide catalyst compounds (or “components”) whose structure can be varied to adjust the properties of the resulting polyolefin, especially polypropylene and polyethylene.

SUMMARY OF THE INVENTION

Disclosed are two classes of pyridyldiamide metal catalyst components, and processes for using these to polymerize olefins, especially α-olefins, to form polyolefins. A first class of pyridyldiamide metal catalyst components is represented by general formula (1) or (2):

Q1is a three atom bridging group described further herein;

Q2is a group that may form a bond with M, including, but not limited to a group 16 element (such as O or S) or NR17or PR17, where R17is selected from hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, aryloxy, halogen, amino, and silyl;

Q3is -(TT)- or -(TTT)-, where each T is carbon or a heteroatom, preferably C, O, S, or N), and said carbon or heteroatom may be unsubstituted (e.g., hydrogen is bound to the carbon or heteroatom) or substituted with one or more R30groups, that, as part of the “—C-Q3=C—” fragment, forms a 5- or 6-membered cyclic group or a polycyclic group including the 5 or 6 membered cyclic group;

R1is selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, silyl, or substituted silyl groups;

R10is -E(R12)(R13)—, with E being carbon, silicon, or germanium, and each R12and R13being independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, silyl, amino, aryloxy, halogen, and phosphino, R12and R13may be joined to form a saturated, substituted or unsubstituted hydrocarbyl ring;

Z is —(R14)pC—C(R15)q—, which is a bridging group, where R14and R15are independently selected from the group consisting of hydrogen, hydrocarbyls, and substituted hydrocarbyls, and wherein adjacent R14and R15groups, having the “C—C” group therebetween, may be joined to form an aromatic or saturated, substituted or unsubstituted hydrocarbyl ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings, p is 1 or 2 and q is 1 or 2;

L is an anionic leaving group, where the L groups may be the same or different and any two L groups may be linked to form a dianionic leaving group, and n is 0, 1, 2, 3, or 4; and

L′ is neutral Lewis base, and w is 0, 1, 2, 3, or 4.

A second class of pyridyldiamide metal catalyst components may be represented by general formula (5) or (6):

DETAILED DESCRIPTION

Unless otherwise indicated, room temperature is 23° C.

As used herein, the numbering scheme for the Periodic Table groups is the new notation as set out in Chemical and Engineering News, 63(5), 27 (1985).

An “olefin,” alternatively referred to as “alkene,” is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond. For purposes of this specification and the claims appended thereto, when a polymer or copolymer is referred to as comprising an olefin, the olefin present in such polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have an “ethylene” content of 35 wt % to 55 wt %, it is understood that the mer unit in the copolymer is derived from ethylene in the polymerization reaction and said derived units are present at 35 wt % to 55 wt %, based upon the weight of the copolymer. A “polymer” has two or more of the same or different mer units. A “homopolymer” is a polymer having mer units that are the same. A “copolymer” is a polymer having two or more mer units that are different from each other. “Different” as used to refer to mer units indicates that the mer units differ from each other by at least one atom or are different isomerically. An “ethylene polymer” or “ethylene copolymer” is a polymer or copolymer comprising at least 50 mol % ethylene derived units, a “propylene polymer” or “propylene copolymer” is a polymer or copolymer comprising at least 50 mol % propylene derived units, and so on.

Pyridyldiamides are known to be good olefin polymerization catalysts. Described herein is a new structural variant that introduces a quaternary carbon center into the ligand backbone at a site that may be prone to unwanted decomposition chemistry. Also, described is a new structural variant that introduces a methyl-substituted phenyl linker group into the ligand backbone. This substitution, relative to the unsubstituted phenyl linker group, leads to catalysts for propylene polymerization that produce polypropylene with higher crystallinity. These catalyst may also be useful in making propylene-based elastomers.

Described herein, broadly, are two classes of pyridyldiamide metal catalyst complexes (or “components”). The first class can be represented by a pyridyldiamide metal catalyst component having the general formula (1) or (2):

M is a Group 3-12 metal, more preferably a Group 4 or 5 metals, and more preferably a zirconium or hafnium, even more preferably a hafnium;

Q1is a three atom bridging group represented by the formula -G1-G2-G3-, each of which may be independently substituted with R30and/or R31groups, where G2is a group 15 or 16 atom, G1and G3are each a group 14, 15, or 16 atom, where G1, G2and G3, or G1and G2, or G1and G3, or G2and G3may form a singular or multi-ring system, and if any of G1and/or G3is a group 14 atom then R30and R31are bound to such G atom(s), and if any of G1, G2and/or G3is a group 15 atom then R30is bound to such G atom(s), where each R30and R31is, independently, hydrogen or a C1to C20or C50or C100hydrocarbyl group; where most preferably Q1of (1) or the Q3ring of (2) form a pyridine ring which may be substituted with C1to C6hydrocarbyls, or unsubstituted hydrocarbyls; and where any one of G1, G2or G3may form a bond, preferably a dative bond, to M;

Q2is a group that forms a bond, preferably an anionic bond, with M, including, but not limited to a group 16 element (such as O or S) or NR17or PR17, where R17is selected from hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, aryloxy, halogen, amino, and silyl; and most preferably Q2forms an aniline, where the nitrogen is bound to the metal, and which may be substituted with C1to C6hydrocarbyls, or unsubstituted hydrocarbyls;

Q3is -(TT)- or -(TTT)-, where each T is carbon or a heteroatom, and each carbon or heteroatom may independently be substituted by hydrogen or one or more R30groups, and as part of the “—C-Q3=C—” fragment forms a 5- or 6-membered cyclic group or a polycyclic group including the 5 or 6 membered cyclic group; and preferably the Q3ring of (2) forms a pyridine ring which may be substituted with C1to C6hydrocarbyls;

R1is selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, silyl, or substituted silyl groups; and is preferably a phenyl or substituted phenyl, and when substituted, the substituents are preferably C1to C6hydrocarbyls, most preferably in the ortho positions;

R10is -E(R12)(R13)— (where it is understood that each of R12and R13are bound to E by a chemical bond), with E being carbon, silicon, or germanium, and each R12and R13being independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, silyl, amino, aryloxy, halogen, and phosphino, R12and R13may be joined to form a saturated, substituted or unsubstituted hydrocarbyl ring, where the ring has 4, 5, 6, or 7 ring carbon atoms and where substitutions on the ring can join to form additional rings, or R12and R13may be joined to form a saturated heterocyclic ring, or a saturated substituted heterocyclic ring where substitutions on the ring can join to form additional rings;

Z is —(R14)pC—C(R15)q—, where R14and R15are independently selected from the group consisting of hydrogen, hydrocarbyls, and substituted hydrocarbyls, and wherein adjacent R14and R15groups, having the “C—C” group therebetween, may be joined to form an aromatic or saturated, substituted or unsubstituted hydrocarbyl ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings, p is 1 or 2 and q is 1 or 2;

L is an anionic leaving group, where the L groups may be the same or different and any two L groups may be linked to form a dianionic leaving group, and n is 0, 1, 2, 3, or 4; preferably L is a C1to C6hydrocarbyl, a C6to C12aryl or substituted aryl, or a halogen; and

L′ is neutral Lewis base, and w is 0, 1, 2, 3, or 4; preferably the “neutral Lewis base” is any neutral molecule that contains a lone pair of electrons that could bind to the catalyst metal center. Typical examples include ethers, thioethers, amines, and/or phosphines.

As used herein, a “hydrocarbyl” is a radical (at least a single radical) made of carbon and hydrogen, in any configuration (branched, linear, cis-, trans-, secondary, tertiary, etc.). A “substituted hydrocarbyl” is a hydrocarbyl that is substituted in one or more positions with a heteroatom or heteroatom group such as a hydroxyl group, carboxy group, ester, amine, silyl, halogen, haloalkyl, etc. Preferably, hydrocarbyls are selected from C1to C6or C10or C12alkyls, C6to C12aryls, and/or C7to C20alkylaryls.

More preferably, the first class of pyridyldiamide metal catalyst components is represented by the formula (3) or (4):

M is a Group 3-5 metal, or as described above for (1) and (2);

R1and R11are independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, silyl groups, or substituted silyl groups;

R10is -E(R12)(R13)—, with E being carbon, silicon, or germanium, and each R12and R13being independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, silyl, amino, aryloxy, halogen, and phosphino, R12and R13may be joined to form a saturated, substituted or unsubstituted hydrocarbyl ring, where the ring has 4, 5, 6, or 7 ring carbon atoms and where substitutions on the ring can join to form additional rings, or R12and R13may be joined to form a saturated heterocyclic ring, or a saturated substituted heterocyclic ring where substitutions on the ring can join to form additional rings;

R3, R4, and R5are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, aryloxy, halogen, amino, and silyl, and wherein adjacent R groups (R3and R4and/or R4and R5) may be joined to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings;

R6, R7, R8, R9, R18, and R19are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen, amino, and silyl, and wherein adjacent R groups (R6and R7, and/or R8and R9, and in (4) R7and R18, and/or R18and R19) may be joined to form a saturated, substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings; and

L and L′, along with n and w, are as described above.

For structures (1) to (4), there are some more preferred configurations. For instance, R10may be selected from C1to C4divalent hydrocarbyls, most preferably a C1or C2alkylene. Preferably, R1is selected from phenyl and substituted phenyl, wherein the substitutions are selected from C1to C5hydrocarbyls, preferably C2to C4hydrocarbyls, and can reside in any of the ortho, meta, para positions on the phenyl ring. Preferably, R11may be selected from phenyl and substituted phenyl, wherein the phenyl substitutions are selected from C1to C5hydrocarbyls, preferably C1hydrocarbyls, and can reside in any of the ortho, meta, para positions on the phenyl ring.

The invention also includes a second class of pyridyldiamide metal catalyst components having the general formula (5) or (6):

M is a Group 3-12 metal; or more preferably as described above for (1) and (2);

Q1, Q2and Q3are as described above for (1) and (2);

R1is selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, silyl, or substituted silyl groups; or as described above for (1) and (2);

R2and R10are each, independently, -E(R12)(R13)—, with E being carbon, silicon, or germanium, and each R12and R13being independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, silyl, amino, aryloxy, halogen, and phosphino, R12and R13may be joined to form a saturated, substituted or unsubstituted hydrocarbyl ring, where the ring has 4, 5, 6, or 7 ring carbon atoms and where substitutions on the ring can join to form additional rings, or R12and R13may be joined to form a saturated heterocyclic ring, or a saturated substituted heterocyclic ring where substitutions on the ring can join to form additional rings; and, more preferably, R2and R10are as described above for (1) and (2); and

L and L′, along with n and w, are as described above.

R2and R10are not required to be substituted, however, one of R2and R10may be asymmetrically substituted while the other is symmetrically substituted, or both may be asymmetrically substituted.

More preferably, the second class of inventive pyridyldiamide metal catalyst components is represented by the formula (7):

M is a Group 3, 4 or 5 metal; and more preferably as described above for (1) and (2);

R1and R11are independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, silyl, or substituted silyl groups;

R2and R10are each, independently, -E(R12)(R13)—, with E being carbon, silicon, or germanium, and each R12and R13being independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, silyl, amino, aryloxy, halogen, and phosphino, R12and R13may be joined to form a saturated, substituted or unsubstituted hydrocarbyl ring, where the ring has 4, 5, 6, or 7 ring carbon atoms and where substitutions on the ring can join to form additional rings, or R12and R13may be joined to form a saturated heterocyclic ring, or a saturated substituted heterocyclic ring where substitutions on the ring can join to form additional rings;

R3, R4, and R5are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, aryloxy, halogen, amino, and silyl, and wherein adjacent R groups (R3and R4, and/or R4and R5) may be joined to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings;

R7, R8, and R9are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen, amino, and silyl, and wherein adjacent R groups (R6and R7and/or R8and R9) may be joined to form a saturated, substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings; and

L and L′, along with n and w, are as described above.

As with (5) and (6) above, R2and R10in (7) are not required to be substituted, however, one of R2and R10may be asymmetrically substituted while the other is symmetrically substituted, or both may be asymmetrically substituted.

For structures (5) to (7), there are some more preferred configurations. For instance, R10is preferably selected from C1to C4divalent hydrocarbyl radicals, most preferably a C1or C2alkylene. Also, R1is preferably selected from phenyl and substituted phenyl, wherein the substitutions are selected from C1to C5hydrocarbyls, preferably C2to C4hydrocarbyls, and can reside in any of the ortho, meta, para positions on the phenyl ring. R11is preferably selected from phenyl and substituted phenyl, wherein the substitutions are selected from C1to C5hydrocarbyls, preferably methyl, and can reside in any of the ortho, meta, para positions on the phenyl ring. And finally, R6is preferably selected from methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, and tert-butyl; most preferably ethyl or methyl.

The pyridyldiamide catalyst components are typically used along with a so-called “NCA” or “MAO” activator, both of which are well known classes of “activators”, to polymerize ethylene and/or C3to C10or C20olefins to form polyolefins, preferably propylene homopolymers and copolymers or ethylene homopolymers and copolymers. Different catalyst components are preferred for propylene polymerization and ethylene polymerization. The catalyst components may be supported, alone or with the activator, and may be used in any polymerization process known in the art, especially solution or slurry polymerization, or combinations of various methods. Further, the catalyst components can be used in one or multiple reactors, and can preferably be used alone, without additional catalyst components, in forming block copolymers. The inventive pyridyldiamide metal catalyst components are particularly useful in higher temperature (relative to metallocene-type catalyst components) polymerization processes, especially those above 70 or 80 or 90° C., up to 120 or 140° C.

The invention thus includes a process to produce polypropylenes, or propylene-based copolymers and elastomers, using a pyridyldiamide metal catalyst component, comprising combining propylene, and optionally ethylene or C4to C12olefins, most preferably 1-butene, 1-hexene or 1-octene, with a catalyst component and activator, the catalyst component comprising (8):

M is a Group 3, 4 or 5 metal; most preferably zirconium or hafnium, and most preferably hafnium;

R1and R11are independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, silyl, or substituted silyl groups;

R2′and R2″are selected independently from hydrogen and C1to C6hydrocarbyls, preferably methyl or hydrogen, most preferably hydrogen; and the other groups are as described above; and

wherein as the steric hindrance created in the R6group, with respect to the R5group, is increased, the peak melting point temperature of the polypropylene produced increases within a range of from 120 or 130° C. to 145 or 150° C.

By “steric hindrance”, what is meant is that characteristic of molecular structure of the catalyst component in which the atoms or groups pendant from the atoms on the catalyst component have a spatial arrangement of the atoms or groups that causes steric strain, or additional energy or molecular bonds due to the peculiar molecular geometry, or, stated another way, strain resulting from van der Vaals repulsion when two atoms or groups in the catalyst component approach each other with a distance less than the sum of their van der Waals radii. Such steric strain is well known in the chemical arts. Thus, in the case of the catalyst component represented in (8), the R5and R6groups may interact such that they cause the rings to which they are attached to bend away from the plane they exist in when both R5and R6are hydrogens.

There are some most preferred configurations for the catalyst component (8). For instance, R2′and R2″are preferably hydrogen or methyl, most preferably hydrogen. Also, R7is preferably hydrogen and R6is selected from methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, and tert-butyl; preferably methyl.

Most preferably, R2′and R2″are each methyl and the activity of the catalyst component is greater than 20,000 or 25,000 g polymer/mmol catalyst/hour, or within the range of from 20,000 or 25,000 or 50,000 g polymer/mmol catalyst/hour to 300,000 or 400,000 or 500,000 g polymer/mmol catalyst/hour. In any case, regardless of the substitutions, the propylene homopolymer or copolymer generated from a process including, or consisting essentially of, or consisting of (8) and an activator, has a molecular weight distribution (Mw/Mn, also referred to as polydispersity index or PDI) of less than 2.5 or 2.2 or 2.0; or within the range of from 1.0 or 1.2 or 1.4 to 2.0 or 2.2. or 2.5.

“Polypropylene(s)” include homopolymers of propylene, copolymers of propylene and ethylene and/or C4to C12α-olefins, or propylene-based elastomers which are also copolymers with ethylene and/or C4to C12α-olefins that may also include dienes. Suitable dienes include, for example: 1,4-hexadiene, 1,6-octadiene, 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, dicyclopentadiene (DCPD), ethylidiene norbornene (ENB), norbornadiene, 5-vinyl-2-norbornene (VNB), and combinations thereof. More particularly, the homopolymers or copolymers of propylene comprise from 60 wt % or 70 wt % or 80 wt % or 85 wt % or 90 wt % or 95 wt % or 98 wt % or 99 wt % to 100 wt % propylene-derived units (and comprising within the range of from 0 wt % or 1 wt % or 5 wt % to 10 wt % or 15 wt % or 20 wt % or 30 wt % or 40 wt % C2and/or C4to C10α-olefin derived units), by weight of the polymer. The propylene-based elastomer, a special case of a copolymer, preferably has a melting point of less than 110° C. or 100° C. or 90° C. or 80° C.; and preferably within the range of from 10° C. or 15° C. or 20° C. or 25° C. to 65° C. or 75° C. or 80° C. or 95° C. or 105° C. or 110° C., and a heat of fusion (Hf), determined according to the Differential Scanning calorimetry (DSC) within the range of from 0.5 J/g or 1 J/g or 5 J/g to 35 J/g or 40 J/g or 50 J/g or 65 J/g or 75 J/g.

The invention also includes a process to produce ethylene copolymers using a pyridyldiamide metal catalyst component, comprising combining ethylene, and C3to C12olefins, preferably propylene, 1-hexene or 1-octene, with a catalyst component and activator, the catalyst component comprising (9):

M is a Group 3-5 metal; preferably zirconium or hafnium, most preferably hafnium;

R1and R11are independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, or silyl groups;

R2′and R2″are selected independently from hydrogen and C1to C6hydrocarbyls, preferably hydrogen; and the other groups are as defined above; and

wherein as the reaction temperature is increased, the peak melting point temperature of the ethylene copolymer produced increases. More preferably, the polymerization of ethylene alone or with comonomers in the presence of (9) can take place at a desirable temperature within the range, wherein the lower reaction temperature range is within the range of from 70 to 90° C. and the upper reaction temperature range is within the range of from 100 to 110° C. and the melting point temperature of the ethylene copolymer increases by at least 5 or 10° C.

“Ethylene copolymers” or ethylene-based polyolefins that comprise at least 50 or 60 or 70 or 80 wt %, by weight of the polymer, of ethylene-derived units.

Preferably, R2′and R2″are hydrogen or methyl, preferably methyl in (9), and preferably R6and R7form an aromatic ring or R7is hydrogen and R6is selected from methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, and tert-butyl, preferably methyl. In any case, regardless of the substitutions, the ethylene homopolymer or copolymer generated from a process including, or consisting essentially of, or consisting of (9) and an activator, has a molecular weight distribution (Mw/Mn) of less than 2.5 or 2.2 or 2.0; or within the range of from 1.0 or 1.2 or 1.4 to 2.0 or 2.2. or 2.5.

After the complexes have been synthesized, catalyst systems may be formed by combining them with activators in any manner known from the literature including by supporting them for use in slurry or gas phase polymerization. The catalyst systems may also be added to or generated in solution polymerization or bulk polymerization (in the monomer). The catalyst system typically comprises a complex as described above and an activator such as alumoxane or a non-coordinating anion. Activation may be performed using alumoxane solution including methyl alumoxane, referred to as MAO, as well as modified MAO, referred to herein as MMAO, containing some higher alkyl groups to improve the solubility. Particularly useful MAO can be purchased from Albemarle in a 10 wt % solution in toluene. The catalyst system employed in the present invention preferably uses an activator selected from alumoxanes, such as methyl alumoxane, modified methyl alumoxane, ethyl alumoxane, iso-butyl alumoxane, and the like.

When an alumoxane or modified alumoxane is used, the complex-to-activator molar ratio is from about 1:3000 to 10:1; alternatively, 1:2000 to 10:1; alternatively 1:1000 to 10:1; alternatively, 1:500 to 1:1; alternatively 1:300 to 1:1; alternatively 1:200 to 1:1; alternatively 1:100 to 1:1; alternatively 1:50 to 1:1; alternatively 1:10 to 1:1. When the activator is an alumoxane (modified or unmodified), some embodiments select the maximum amount of activator at a 5000-fold molar excess over the catalyst precursor (per metal catalytic site). The preferred minimum activator-to-complex ratio is 1:1 molar ratio.

Activation may also be performed using non-coordinating anions, referred to as NCA's, of the type described in EP 277 003 A1 and EP 277 004 A1. NCA may be added in the form of an ion pair using, for example, [DMAH]+[NCA]−in which the N,N-dimethylanilinium (DMAH) cation reacts with a basic leaving group on the transition metal complex to form a transition metal complex cation and [NCA]−. The cation in the precursor may, alternatively, be trityl. Alternatively, the transition metal complex may be reacted with a neutral NCA precursor, such as B(C6F5)3, which abstracts an anionic group from the complex to form an activated species. Useful activators include N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (i.e., [PhNMe2H]B(C6F5)4) and N,N-dimethylanilinium tetrakis(heptafluoronaphthyl)borate, where Ph is phenyl, and Me is methyl.

Additionally, preferred activators useful herein include those described in U.S. Pat. No. 7,247,687 at column 169, line 50 to column 174, line 43, particularly column 172, line 24 to column 173, line 53.

Alternately, a co-activator may also be used in the catalyst system herein. The complex-to-co-activator molar ratio is from 1:100 to 100:1; 1:75 to 75:1; 1:50 to 50:1; 1:25 to 25:1; 1:15 to 15:1; 1:10 to 10:1; 1:5 to 5:1, 1:2 to 2:1; 1:100 to 1:1; 1:75 to 1:1; 1:50 to 1:1; 1:25 to 1:1; 1:15 to 1:1; 1:10 to 1:1; 1:5 to 1:1; 1:2 to 1:1; 1:10 to 2:1.

The term “non-coordinating anion” (NCA) means an anion which either does not coordinate to a cation or which is only weakly coordinated to a cation thereby remaining sufficiently labile to be displaced by a neutral Lewis base. “Compatible” non-coordinating anions are those which are not degraded to neutrality when the initially formed complex decomposes. Further, the anion will not transfer an anionic substituent or fragment to the cation so as to cause it to form a neutral transition metal compound and a neutral by-product from the anion. Non-coordinating anions useful in accordance with this invention are those that are compatible, stabilize the transition metal cation in the sense of balancing its ionic charge at +1, and yet retain sufficient lability to permit displacement during polymerization.

It is within the scope of this invention to use an ionizing or stoichiometric activator, neutral or ionic, such as tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, a tris perfluorophenyl boron metalloid precursor or a tris perfluoronaphthyl boron metalloid precursor, polyhalogenated heteroborane anions (WO 98/43983), boric acid (U.S. Pat. No. 5,942,459), or combination thereof. It is also within the scope of this invention to use neutral or ionic activators alone or in combination with alumoxane or modified alumoxane activators.

Examples of neutral stoichiometric activators include tri-substituted boron, tellurium, aluminum, gallium, and indium, or mixtures thereof. The three substituent groups are each independently selected from alkyls, alkenyls, halogens, substituted alkyls, aryls, arylhalides, alkoxy, and halides. Preferably, the three groups are independently selected from halogen, mono or multicyclic (including halosubstituted) aryls, alkyls, and alkenyl compounds, and mixtures thereof, preferred are alkenyl groups having 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms and aryl groups having 3 to 20 carbon atoms (including substituted aryls). More preferably, the three groups are alkyls having 1 to 4 carbon groups, phenyl, naphthyl, or mixtures thereof. Even more preferably, the three groups are halogenated, preferably fluorinated, aryl groups. A preferred neutral stoichiometric activator is tris perfluorophenyl boron or tris perfluoronaphthyl boron.

Preferred compounds useful as an activator in the process of this invention comprise a cation, which is preferably a Bronsted acid capable of donating a proton, and a compatible non-coordinating anion which anion is relatively large (bulky), capable of stabilizing the active catalyst species (the Group 4 cation) which is formed when the two compounds are combined and said anion will be sufficiently labile to be displaced by olefinic, diolefinic and acetylenically unsaturated substrates or other neutral Lewis bases, such as ethers, amines, and the like. Two classes of useful compatible non-coordinating anions have been disclosed in EP 0 277 003 A1 and EP 0 277 004 A1: 1) anionic coordination complexes comprising a plurality of lipophilic radicals covalently coordinated to and shielding a central charge-bearing metal or metalloid core; and 2) anions comprising a plurality of boron atoms such as carboranes, metallacarboranes, and boranes.

In a preferred embodiment, the stoichiometric activators include a cation and an anion component, and are preferably represented by the following formula (II):
(Z)d+(Ad−)  (II)
wherein Z is (L-H) or a reducible Lewis Acid, L is a neutral Lewis base; H is hydrogen; (L-H)+is a Bronsted acid; Ad−is a non-coordinating anion having the charge d−; and d is an integer from 1 to 3.

When Z is (L-H) such that the cation component is (L-H)d+, the cation component may include Bronsted acids such as protonated Lewis bases capable of protonating a moiety, such as an alkyl or aryl, from the bulky ligand metallocene containing transition metal catalyst precursor, resulting in a cationic transition metal species. Preferably, the activating cation (L-H)d+is a Bronsted acid, capable of donating a proton to the transition metal catalytic precursor resulting in a transition metal cation, including ammoniums, oxoniums, phosphoniums, silyliums, and mixtures thereof, preferably ammoniums of methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine, triphenylphosphine, and diphenylphosphine, oxoniums from ethers, such as dimethyl ether diethyl ether, tetrahydrofuran, and dioxane, sulfoniums from thioethers, such as diethyl thioethers and tetrahydrothiophene, and mixtures thereof.

When Z is a reducible Lewis acid, it is preferably represented by the formula: (Ar3C+), where Ar is aryl or aryl substituted with a heteroatom, a C1to C40hydrocarbyl, or a substituted C1to C40hydrocarbyl, preferably the reducible Lewis acid is represented by the formula: (Ph3C+), where Ph is phenyl or phenyl substituted with a heteroatom, a C1to C40hydrocarbyl, or a substituted C1to C40hydrocarbyl. In a preferred embodiment, the reducible Lewis acid is triphenyl carbenium.

The anion component Ad−includes those having the formula [Mk+Qn]d−wherein k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6, preferably 3, 4, 5 or 6; n−k=d; M is an element selected from Group 13 of the Periodic Table of the Elements, preferably boron or aluminum, and Q is independently a hydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, and halosubstituted-hydrocarbyl radicals, said Q having up to 20 carbon atoms with the proviso that in not more than one occurrence is Q a halide, and two Q groups may form a ring structure. Preferably, each Q is a fluorinated hydrocarbyl group having 1 to 20 carbon atoms, more preferably each Q is a fluorinated aryl group, and most preferably each Q is a pentafluoryl aryl group. Examples of suitable Ad−components also include diboron compounds as disclosed in U.S. Pat. No. 5,447,895, which is fully incorporated herein by reference.

In a preferred embodiment, this invention relates to a method to polymerize olefins comprising contacting olefins (preferably ethylene and or propylene) with the catalyst compound and a boron containing NCA activator represented by the formula (14):
Zd+(Ad−)  (14)
where: Z is (L-H) or a reducible Lewis acid; L is a neutral Lewis base (as further described above); H is hydrogen; (L-H) is a Bronsted acid (as further described above); A−is a boron containing non-coordinating anion having the charge d−(as further described above); d is 1, 2, or 3.

In a preferred embodiment in any NCA's represented by Formula 14 described above, the reducible Lewis acid is represented by the formula: (Ar3C+), where Ar is aryl or aryl substituted with a heteroatom, a C1to C40hydrocarbyl, or a substituted C1to C40hydrocarbyl, preferably the reducible Lewis acid is represented by the formula: (Ph3C+), where Ph is phenyl or phenyl substituted with a heteroatom, a C1to C40hydrocarbyl, or a substituted C1to C40hydrocarbyl.

In a preferred embodiment in any of the NCA's represented by Formula 14 described above, Zd+is represented by the formula: (L-H)d+, wherein L is a neutral Lewis base; H is hydrogen; (L-H) is a Bronsted acid; and d is 1, 2, or 3, preferably (L-H)d+is a Bronsted acid selected from ammoniums, oxoniums, phosphoniums, silyliums, and mixtures thereof.

In a preferred embodiment in any of the NCA's represented by Formula 14 described above, the anion component Ad−is represented by the formula [M*k*+Q*n*]d*−wherein k* is 1, 2, or 3; n* is 1, 2, 3, 4, 5, or 6 (preferably 1, 2, 3, or 4); n*−k*=d*; M* is boron; and Q* is independently selected from hydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, and halosubstituted-hydrocarbyl radicals, said Q* having up to 20 carbon atoms with the proviso that in not more than 1 occurrence is Q* a halide.

This invention also relates to a method to polymerize olefins comprising contacting olefins (such as ethylene and or propylene) with the catalyst compound and an NCA activator represented by the formula (I):
RnM**(ArNHal)4-n(I)
where R is a monoanionic ligand; M** is a Group 13 metal or metalloid; ArNHal is a halogenated, nitrogen-containing aromatic ring, polycyclic aromatic ring, or aromatic ring assembly in which two or more rings (or fused ring systems) are joined directly to one another or together; and n is 0, 1, 2, or 3. Typically the NCA comprising an anion of Formula I also comprises a suitable cation that is essentially non-interfering with the ionic catalyst complexes formed with the transition metal compounds, preferably the cation is Zd+as described above.

In a preferred embodiment in any of the NCA's comprising an anion represented by Formula I described above, R is selected from the group consisting of substituted or unsubstituted C1to C30hydrocarbyl aliphatic or aromatic groups, where substituted means that at least one hydrogen on a carbon atom is replaced with a hydrocarbyl, halide, halocarbyl, hydrocarbyl or halocarbyl substituted organometalloid, dialkylamido, alkoxy, aryloxy, alkysulfido, arylsulfido, alkylphosphido, arylphosphide, or other anionic substituent; fluoride; bulky alkoxides, where bulky means C4to C20hydrocarbyl groups; —SR1, —NR22, and —PR32, where each R1, R2, or R3is independently a substituted or unsubstituted hydrocarbyl as defined above; or a C1to C30hydrocarbyl substituted organometalloid.

In a preferred embodiment in any of the NCA's comprising an anion represented by Formula I described above, the NCA also comprises cation comprising a reducible Lewis acid represented by the formula: (Ar3C+), where Ar is aryl or aryl substituted with a heteroatom, a C1to C40hydrocarbyl, or a substituted C1to C40hydrocarbyl, preferably the reducible Lewis acid represented by the formula: (Ph3C+), where Ph is phenyl or phenyl substituted with a heteroatom, a C1to C40hydrocarbyl, or a substituted C1to C40hydrocarbyl.

In a preferred embodiment in any of the NCA's comprising an anion represented by Formula I described above, the NCA also comprises a cation represented by the formula, (L-H)d+, wherein L is a neutral Lewis base; H is hydrogen; (L-H) is a Bronsted acid; and d is 1, 2, or 3, preferably (L-H)d+is a Bronsted acid selected from ammoniums, oxoniums, phosphoniums, silyliums, and mixtures thereof.

Further examples of useful activators include those disclosed in U.S. Pat. Nos. 7,297,653 and 7,799,879.

Another activator useful herein comprises a salt of a cationic oxidizing agent and a noncoordinating, compatible anion represented by the formula (16):
(OXe+)d(Ad−)e(16)
wherein OXe+is a cationic oxidizing agent having a charge of e+; e is 1, 2, or 3; d is 1, 2 or 3; and Ad−is a non-coordinating anion having the charge of d− (as further described above). Examples of cationic oxidizing agents include: ferrocenium, hydrocarbyl-substituted ferrocenium, Ag+, or Pb+2. Preferred embodiments of Ad−include tetrakis(pentafluorophenyl)borate.

In another embodiment, the catalyst compounds can be used with Bulky activators. A “Bulky activator” as used herein refers to anionic activators represented by the formula:

where:
each R1is, independently, a halide, preferably a fluoride;
each R2is, independently, a halide, a C6to C20substituted aromatic hydrocarbyl group or a siloxy group of the formula —O—Si—Ra, where Rais a C1to C20hydrocarbyl or hydrocarbylsilyl group (preferably R2is a fluoride or a perfluorinated phenyl group);
each R3is a halide, C6to C20substituted aromatic hydrocarbyl group or a siloxy group of the formula —O—Si—Ra, where Rais a C1to C20hydrocarbyl or hydrocarbylsilyl group (preferably R3is a fluoride or a C6perfluorinated aromatic hydrocarbyl group); wherein R2and R3can form one or more saturated or unsaturated, substituted or unsubstituted rings (preferably R2and R3form a perfluorinated phenyl ring);
L is a neutral Lewis base; (L-H)+is a Bronsted acid; d is 1, 2, or 3;
wherein the anion has a molecular weight of greater than 1020 g/mol; and
wherein at least three of the substituents on the B atom each have a molecular volume of greater than 250 cubic Å, alternately greater than 300 cubic Å, or alternately greater than 500 cubic Å.

“Molecular volume” is used herein as an approximation of spatial steric bulk of an activator molecule in solution. Comparison of substituents with differing molecular volumes allows the substituent with the smaller molecular volume to be considered “less bulky” in comparison to the substituent with the larger molecular volume. Conversely, a substituent with a larger molecular volume may be considered “more bulky” than a substituent with a smaller molecular volume.

Molecular volume may be calculated as reported in “A Simple “Back of the Envelope” Method for Estimating the Densities and Molecular Volumes of Liquids and Solids,” Journal of Chemical Education, Vol. 71, No. 11, November 1994, pp. 962-964. Molecular volume (MV), in units of cubic Å, is calculated using the formula: MV=8.3VS, where VSis the scaled volume. VSis the sum of the relative volumes of the constituent atoms, and is calculated from the molecular formula of the substituent using the following table of relative volumes. For fused rings, the VSis decreased by 7.5% per fused ring.

Exemplary bulky substituents of activators suitable herein and their respective scaled volumes and molecular volumes are shown in the table below. The dashed bonds indicate binding to boron, as in the general formula above.

Supports

In some embodiments, the complexes described herein may be supported (with or without an activator) by any method effective to support other coordination catalyst systems, effective meaning that the catalyst so prepared can be used for oligomerizing or polymerizing olefin in a heterogeneous process. The catalyst precursor, activator, co-activator if needed, suitable solvent, and support may be added in any order or simultaneously. Typically, the complex and activator may be combined in solvent to form a solution. Then the support is added, and the mixture is stirred for 1 minute to 10 hours. The total solution volume may be greater than the pore volume of the support, but some embodiments limit the total solution volume below that needed to form a gel or slurry (about 90% to 400%, preferably about 100-200% of the pore volume). After stirring, the residual solvent is removed under vacuum, typically at ambient temperature and over 10-16 hours. But greater or lesser times and temperatures are possible.

The complex may also be supported absent the activator; in that case, the activator (and co-activator if needed) is added to a polymerization process's liquid phase. Additionally, two or more different complexes may be placed on the same support. Likewise, two or more activators or an activator and co-activator may be placed on the same support.

Suitable solid particle supports are typically comprised of polymeric or refractory oxide materials, each being preferably porous. Preferably any support material that has an average particle size greater than 10 μm is suitable for use in this invention. Various embodiments select a porous support material, such as for example, talc, inorganic oxides, inorganic chlorides, for example magnesium chloride and resinous support materials such as polystyrene polyolefin or polymeric compounds or any other organic support material and the like. Some embodiments select inorganic oxide materials as the support material including Group-2, -3, -4, -5, -13, or -14 metal or metalloid oxides. Some embodiments select the catalyst support materials to include silica, alumina, silica-alumina, and their mixtures. Other inorganic oxides may serve either alone or in combination with the silica, alumina, or silica-alumina. These are magnesia, titania, zirconia, and the like. Lewis acidic materials such as montmorillonite and similar clays may also serve as a support. In this case, the support can optionally double as the activator component, however, an additional activator may also be used.

The support material may be pretreated by any number of methods. For example, inorganic oxides may be calcined, chemically treated with dehydroxylating agents such as aluminum alkyls and the like, or both.

Polymeric carriers will also be suitable in accordance with the invention, see for example the descriptions in WO 95/15815 and U.S. Pat. No. 5,427,991. The methods disclosed may be used with the catalyst complexes, activators or catalyst systems of this invention to adsorb or absorb them on the polymeric supports, particularly if made up of porous particles, or may be chemically bound through functional groups bound to or in the polymer chains.

Useful supports typically have a surface area of from 10-700 m2/g, a pore volume of 0.1-4.0 cc/g and an average particle size of 10-500 μm. Some embodiments select a surface area of 50-500 m2/g, a pore volume of 0.5-3.5 cc/g, or an average particle size of 20-200 μm. Other embodiments select a surface area of 100-400 m2/g, a pore volume of 0.8-3.0 cc/g, and an average particle size of 30-100 μm. Useful supports typically have a pore size of 10-1000 Angstroms, alternatively 50-500 Angstroms, or 75-350 Angstroms.

The catalyst complexes described herein are generally deposited on the support at a loading level of 10-100 micromoles of complex per gram of solid support; alternately 20-80 micromoles of complex per gram of solid support; or 40-60 micromoles of complex per gram of support. But greater or lesser values may be used provided that the total amount of solid complex preferably does not exceed the support's pore volume.

Polymerization

Inventive catalyst complexes are useful in polymerizing unsaturated monomers conventionally known to undergo metallocene-catalyzed polymerization such as solution, slurry, gas-phase, and high-pressure polymerization. Typically one or more of the complexes described herein, one or more activators, and one or more monomers are contacted to produce polymer. In certain embodiments, the complexes may be supported and as such will be particularly useful in the known, fixed-bed, moving-bed, fluid-bed, slurry, solution, or bulk operating modes conducted in single, series, or parallel reactors.

One or more reactors in series or in parallel may be used in the present invention. The complexes, activator and when required, co-activator, may be delivered as a solution or slurry, either separately to the reactor, activated in-line just prior to the reactor, or preactivated and pumped as an activated solution or slurry to the reactor. Polymerizations are carried out in either single reactor operation, in which monomer, comonomers, catalyst/activator/co-activator, optional scavenger, and optional modifiers are added continuously to a single reactor or in series reactor operation, in which the above components are added to each of two or more reactors connected in series. The catalyst components can be added to the first reactor in the series. The catalyst component may also be added to both reactors, with one component being added to first reactor and another component to other reactors. In one preferred embodiment, the complex is activated in the reactor in the presence of olefin.

In a particularly preferred embodiment, the polymerization process is a continuous process.

Polymerization processes used herein typically comprise contacting one or more alkene monomers with the complexes (and, optionally, activator) described herein. For purpose of this invention, alkenes are defined to include multi-alkenes (such as dialkenes) and alkenes having just one double bond. Polymerization may be homogeneous (solution or bulk polymerization) or heterogeneous (slurry-in a liquid diluent, or gas phase-in a gaseous diluent). In the case of heterogeneous slurry or gas phase polymerization, the complex and activator may be supported. Silica is useful as a support herein. Chain transfer agents (such as hydrogen, or diethyl zinc) may be used in the practice of this invention.

The present polymerization processes may be conducted under conditions preferably including a temperature of about 30° C. to about 200° C., preferably from 60° C. to 195° C., preferably from 75° C. to 190° C. The process may be conducted at a pressure of from 0.05 MPa to 1500 MPa. In a preferred embodiment, the pressure is between 1.7 MPa and 30 MPa, or in another embodiment, especially under supercritical conditions, the pressure is between 15 MPa and 1500 MPa.

Polymer Products

While the molecular weight of the polymers produced herein is influenced by reactor conditions including temperature, monomer concentration and pressure, the presence of chain terminating agents and the like, the homopolymer and copolymer products produced by the present process may have an Mw of about 1,000 to about 2,000,000 g/mol, alternately of about 30,000 to about 600,000 g/mol, or alternately of about 100,000 to about 500,000 g/mol, as determined by GPC. Preferred polymers produced here may be homopolymers or copolymers. In a preferred embodiment, the comonomer(s) are present at up to 50 mol %, preferably from 0.01 to 40 mol %, preferably 1 to 30 mol %, preferably from 5 to 20 mol %.

Articles made using polymers produced herein may include, for example, molded articles (such as containers and bottles, e.g., household containers, industrial chemical containers, personal care bottles, medical containers, fuel tanks, and storageware, toys, sheets, pipes, tubing) films, non-wovens, and the like. It should be appreciated that the list of applications above is merely exemplary, and is not intended to be limiting.

Having described the various features of the pyridyldiamide metal catalyst components and their use in olefin polymerization, described herein in numbered embodiments, referring by number to the chemical structures, are:1. A pyridyldiamide metal catalyst component having the general formula (1) or (2):

having the features as described herein.2. The pyridyldiamide metal catalyst component of numbered embodiment 1, wherein the catalyst component is represented by the formula (3) or (4):

having the features described herein.3. The pyridyldiamide metal catalyst component of numbered embodiments 1 or 2, wherein R10is selected from C1to C4divalent hydrocarbyls, most preferably a C1or C2alkylene.4. The pyridyldiamide metal catalyst component of any one of the previous numbered embodiments, wherein R1is selected from phenyl and substituted phenyl, wherein the substitutions are selected from C1to C5hydrocarbyls, preferably C2to C4hydrocarbyls, and can reside in any of the ortho, meta, para positions on the phenyl ring.5. The pyridyldiamide metal catalyst component of any one of the previous numbered embodiments, wherein R11is selected from phenyl and substituted phenyl, wherein the substitutions are selected from C1to C5hydrocarbyls, preferably C1hydrocarbyls, and can reside in any of the ortho, meta, para positions on the phenyl ring.6. The pyridyldiamide metal catalyst component of any one of the previous numbered embodiments, wherein M is hafnium or zirconium, preferably hafnium.7. A process to produce olefins comprising combining the pyridyldiamide metal catalyst component of any one of the previous numbered embodiments with any one or combination of ethylene and C3to C12olefins at a temperature from 60 or 65° C. to 120 or 140° C.8. A pyridyldiamide metal catalyst component having the general formula (5) or (6):

having the features described herein.9. The pyridyldiamide metal catalyst component of numbered embodiment 8, wherein the catalyst component is represented by the formula (7):

having the features described herein.10. The pyridyldiamide metal catalyst component of numbered embodiments 8 or 9, wherein R10is selected from C1to C4divalent hydrocarbyl radicals.11. The pyridyldiamide metal catalyst component of any one of numbered embodiments 8-10, wherein R1is selected from phenyl and substituted phenyl, wherein the substitutions are selected from C1to C5hydrocarbyls, preferably C2to C4hydrocarbyls, and can reside in any of the ortho, meta, para positions on the phenyl ring.12. The pyridyldiamide metal catalyst component of any one of numbered embodiments 8-11, wherein R11is selected from phenyl and substituted phenyl, wherein the substitutions are selected from C1to C5hydrocarbyls, preferably methyl, and can reside in any of the ortho, meta, para positions on the phenyl ring.13. The pyridyldiamide metal catalyst component of any one of numbered embodiments 8-12, wherein R6is selected from methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, and tert-butyl; preferably methyl; or alternatively, in numbered embodiment 10, R6and R7are hydrocarbyls that are joined together to form an aryl ring.14. The pyridyldiamide metal catalyst component of any one of numbered embodiments 8-13, wherein M is hafnium or zirconium, preferably hafnium.15. A process to produce polyolefins comprising combining the pyridyldiamide metal catalyst component of any one of numbered embodiments 8-14 with any one or combination of ethylene and C3to C12olefins at a temperature from 60 or 65 or 70 or 75 or 80 or 85° C. to 120 or 140° C.16. A process to produce polyolefins comprising combining the pyridyldiamide metal catalyst component of any one of numbered embodiments 8-15 wherein the polyolefin (preferably polypropylene) has a molecular weight distribution (Mw/Mn) of less than 2.5 or 2.2 or 2.0; or within the range of from 1.0 or 1.2 or 1.4 to 2.0 or 2.2. or 2.5.17. A process to produce polyolefins comprising combining the pyridyldiamide metal catalyst component of any one of numbered embodiments 8-16 wherein R2′and R2″are each methyl and the activity of the catalyst component is greater than 20,000 or 25,000 g polymer/mmol catalyst/hour, or within the range of from 20,000 or 25,000 or 50,000 g polymer/mmol catalyst/hour to 300,000 or 400,000 or 500,000 g polymer/mmol catalyst/hour.18. A process to produce polyolefins, preferably polypropylene, comprising combining the pyridyldiamide metal catalyst component of any one of numbered embodiments 8-17 wherein the lower reaction temperature range is within the range of from 70 to 90° C. and the upper reaction temperature range is within the range of from 100 to 110° C. and the melting point temperature of the ethylene copolymer increases by at least 5 or 10° C.19. The use of the pyridyldiamide metal catalyst component (1), (2), (5), or (6) to polymerize ethylene or propylene alone or with any one or more C4to C12olefins to produce ethylene or propylene homopolymers and copolymers.

The various descriptive elements and numerical ranges disclosed herein for the process, the catalyst component, and the copolymers can be combined with other descriptive elements and numerical ranges to describe the invention(s); further, for a given element, any upper numerical limit can be combined with any lower numerical limit described herein. The features of the invention are described in the following non-limiting examples.

EXAMPLES

The following is a description of the inventive and “comparative” catalyst components, shown inFIG. 1. The ligands are called “L1-H2”, etc., while the catalyst components (metal-ligand complexes) are called “L1HfMe2”, etc. Complexes L7HfMe2and L9HfMe2are used to demonstrate the usefulness of the intermediately substituted “R6” group demonstrated herein.

Synthesis of ligand for MPN3-L2

To 200 ml (0.21 mol) of 1.07 M solution of 2-methyl phenylmagnesiumbromide in THF, 49.3 g (0.27 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added at room temperature. The resulting solution was stirred for 15 min at the same temperature, and then 50 ml of water was added. The formed mixture was poured into 500 ml of water, and crude product was extracted with 3×200 ml of ethyl acetate. The combined organic extract was dried over Na2SO4and then evaporated to dryness. Fractional distillation of the residue in vacuum gave colorless oil, b.p. 81-84° C./3 mmm Hg. Yield 33.1 g (57%). Anal. calc. for C13H19BO2: C, 71.59; H, 8.78. Found: C, 71.78; H, 8.65.1H NMR (CDCl3): 7.78 (m, 1H, 6-H), 7.33 (m, 1H, 5-H), 7.16-7.19 (m, 2H, 3, 4-H), 2.56 (s, 3H, Me in 2-MeC6H4), 1.36 (s, 12H, Bpin).

Synthesis of group 4 pyridyldiamides

The preparation of group 4 pyridyldiamides are described below. The general synthetic route described here involves the reaction of the pryridyldiamine ligand with a group 4 metal amide precursor to afford a pyridyldiamide metal dichloride complex, which can then be subsequently reacted with a dialkylmagnesium, grignard, or alkyllithium reagent to afford precatalysts suitable for activation with typical non-coordinating anion activators (e.g., N,N-dimethylanilinium tetrakis(pentafluorophenylborate). Another useful synthetic route to group 4 pyridyldiamidedichloride complexes (i.e., (pyridyldiamide)MCl2, where M=group 4 metal) is the reaction of a pre-formed or in situ formed dilithiopyridyldiamide species with a group 4 halide.

Synthesis of L1HfCl2

Synthesis of L1HfMe2

Synthesis of L2HfMe2

Synthesis of L3HfMe2

Synthesis of L4HfMe2

Synthesis of L5HfMe2

Synthesis of L7HfMe2

Toluene (6 mL) was added to L7H2(0.194 g, 0.418 mmol) and Hf(NMe2)2Cl2(dme) (0.179 g, 0.418 mmol) to form a pale yellow solution. The mixture was loosely capped with aluminum foil and heated to 95° C. After 2.5 hours the volatiles were removed with a stream of nitrogen. Then Et2O (5 mL) was added and the mixture was stirred to give an off-white suspension. The solid was collected by filtration and dried under reduced pressure to afford 0.233 g of presumed dichloride (i.e., L7HfCl2) product. Methylene chloride (7 mL) was added to the dichloride and the mixture was cooled to −40° C. An Et2O solution of Me2Mg (1.67 mL, 0.393 mmol) was then added dropwise and the mixture was allowed to warm to ambient temperature. After reaching ambient temperature the volatiles were removed under a stream of nitrogen. The crude product was extracted with CH2Cl2(5 mL) and filtered. Most of the CH2Cl2was evaporated and hexanes (3 mL) were added to afford a suspension. The pale pink solid was isolated by filtration and dried under reduced pressure at 45° C. Yield: 0.239 g, 85.3%.1H NMR (CD2Cl2): δ 8.01 (t, 1H), 7.6-6.8 (m, 13H), 5.03 (br AB quartet, 2H, Δυ=247 Hz, J=20 Hz), 4.50 (br, 1H), 4.03 (br, 1H), 3.73 (br, 1H), 3.15 (br, 1H), 2.34 (br, 3H), 1.16 (d, 9H), 0.68 (s, 3H), −0.72 (s, 3H), −0.84 (s, 3H).

Synthesis of L8HfMe2

Toluene (6 mL) was added to L8H2(0.248 g, 0.519 mmol) and Hf(NMe2)2Cl2(dme) (0.222 g, 0.519 mmol) to form a pale yellow solution. The mixture was loosely capped with aluminum foil and heated to 95° C. After 2.5 hours the volatiles were removed with a stream of nitrogen. Then Et2O (5 mL) was added and the mixture was stirred to give an off-white suspension. The solid was collected by filtration and dried under reduced pressure to afford 0.355 g of presumed dichloride (i.e., L8HfCl2) product. Methylene chloride (7 mL) was added to the dichloride and the mixture was cooled to −40° C. An Et2O solution of Me2Mg (2.50 mL, 0.588 mmol) was then added dropwise and the mixture was allowed to warm to ambient temperature. After reaching ambient temperature the volatiles were removed under a stream of nitrogen. The crude product was extracted with CH2Cl2(5 mL) and filtered. The volatiles were evaporated and the resulting off-white solid was dried under reduced pressure. Yield: 0.315 g, 88.7%.1H NMR (CD2Cl2): δ 7.99 (t, 1H), 7.50-6.93 (m, 12H), 5.01 (AB quartet, 2H, Δυ=141 Hz, J=21 Hz), 4.22 (br, 1H), 3.98 (br, 1H), 3.81 (sept, 1H), 2.96 (br, 1H), 2.24 (br, 3H), 2.22 (s, 3H), 1.18 (m, 6H), 1.12 (d, 3H), 0.55 (d, 3H), −0.76 (br, 3H), −0.81 (s, 3H).

Synthesis of L9HfMe2

Toluene (50 mL) was added to L9H2(2.07 g, 4.03 mmol) and Hf(NMe2)2Cl2(dme) (1.73 g, 4.03 mmol) to form a yellow solution. The mixture was loosely capped with aluminum foil and heated to 95° C. After 2.5 hours the solution was cooled to ambient temperature for a couple of hours. The resulting solid was collected on a glass frit, washed with toluene (2×5 mL) and dried under reduced pressure to afford 2.40 g of the dichloride (i.e., L9HfCl2) product with 0.5 equivalents of co-crystallized toluene. Methylene chloride (50 mL) was added to the dichloride and the mixture was cooled to −40° C. An Et2O solution of Me2Mg (15.3 mL, 3.59 mmol) was then added dropwise and the mixture was allowed to warm to ambient temperature. After stirring at ambient temperature for 0.5 hours the volatiles were removed under a stream of nitrogen. The crude product was extracted with CH2Cl2(20 mL) and filtered. The CH2Cl2was evaporated to afford a solid that was washed with pentane (2×10 mL) and dried under reduced pressure. Yield: 2.01 g, 69.2%.1H NMR (CD2Cl2): δ 8.2-6.9 (m, 16H), 5.06 (AB quartet, 2H, Δυ=162 Hz, J=26 Hz), 4.97 (br, 1H), 4.14 (br, 1H), 3.73 (sept, 1H), 3.02 (br, 1H), 2.30 (br, 3H), 1.4-1.0 (m, 9H), 0.89 (t, 2H), 0.55 (d, 3H), −0.80 (s, 3H), −1.14 (s, 3H).

General Polymerization Procedures

Unless stated otherwise, propylene homopolymerizations and ethylene-propylene copolymerizations were carried out in a parallel, pressure reactor, as generally described in U.S. Pat. No. 6,306,658; U.S. Pat. No. 6,455,316; U.S. Pat. No. 6,489,168; WO 00/09255; and Murphy et al., 125 J. AM. CHEM. SOC., pp. 4306-4317 (2003), each of which is fully incorporated herein by reference for US purposes. Although the specific quantities, temperatures, solvents, reactants, reactant ratios, pressures, and other variables are frequently changed from one polymerization run to the next, the following describes a typical polymerization performed in a parallel, pressure reactor.

A pre-weighed glass vial insert and disposable stirring paddle were fitted to each reaction vessel of the reactor, which contains 48 individual reaction vessels. The reactor was then closed and propylene (typically 1 mL) was introduced to each vessel as a condensed gas liquid. If ethylene was added as a comonomer, it was added before the propylene as a gas to a pre-determined pressure (typically 10-80 psi) while the reactor vessels were heated to a set temperature (typically 40° C.). Then solvent (typically isohexane) was added to bring the total reaction volume, including the subsequent additions, to 5 mL and the reactor vessels were heated to their set temperature (usually between 50° C. and 110° C.). At this time scavenger and/or co-catalyst and/or a chain transfer agent, such as tri-n-octylaluminum in toluene (typically 100-1000 Nmol), was added.

The contents of the vessel were stirred at 800 rpm. An activator solution (typically 1.0-1.2 molar equivalents of dimethyl anilinium tetrakis-pentafluorophenyl borate dissolved in toluene or 100-1000 molar equivalents of methyl alumoxane (MAO) in toluene) was then injected into the reaction vessel along with 500 microliters of toluene, followed by a toluene solution of catalyst (typically 0.40 mM in toluene, usually 20-40 nanomols of catalyst) and another aliquot of toluene (500 microliters). Equivalence is determined based on the mol equivalents relative to the moles of the transition metal in the catalyst component.

The reaction was then allowed to proceed until a pre-determined amount of pressure had been taken up by the reaction. Alternatively, the reaction may be allowed to proceed for a set amount of time. At this point, the reaction was quenched by pressurizing the vessel with compressed air. After the polymerization reaction, the glass vial insert containing the polymer product and solvent was removed from the pressure cell and the inert atmosphere glove box, and the volatile components were removed using a Genevac HT-12 centrifuge and Genevac VC3000D vacuum evaporator operating at elevated temperature and reduced pressure. The vial was then weighed to determine the yield of the polymer product. The resultant polymer was analyzed by Rapid GPC (see below) to determine the molecular weight, by FT-IR (see below) to determine percent ethylene incorporation, and by DSC (see below) to determine melting point.

To determine various molecular weight related values by GPC, high temperature size exclusion chromatography was performed using an automated “Rapid GPC” system as generally described in U.S. Pat. No. 6,491,816; U.S. Pat. No. 6,491,823; U.S. Pat. No. 6,475,391; U.S. Pat. No. 6,461,515; U.S. Pat. No. 6,436,292; U.S. Pat. No. 6,406,632; U.S. Pat. No. 6,175,409; U.S. Pat. No. 6,454,947; U.S. Pat. No. 6,260,407; and U.S. Pat. No. 6,294,388. This apparatus has a series of three 30 cm×7.5 mm linear columns, each containing PLgel 10 um, Mix B. The GPC system was calibrated using polystyrene standards ranging from 580-3,390,000 g/mol. The system was operated at an eluent flow rate of 2.0 mL/minutes and an oven temperature of 165° C. 1,2,4-trichlorobenzene was used as the eluent. The polymer samples were dissolved in 1,2,4-trichlorobenzene at a concentration of 0.1-0.9 mg/mL. 250 uL of a polymer solution was injected into the system. The concentration of the polymer in the eluent was monitored using an evaporative light scattering detector. The molecular weights presented are relative to linear polystyrene standards and are uncorrected.

Differential Scanning calorimetry (DSC) measurements were performed on a TA-Q100 instrument to determine the melting point of the polymers. Samples were pre-annealed at 220° C. for 15 minutes and then allowed to cool to room temperature overnight. The samples were then heated to 220° C. at a rate of 100° C./min and then cooled at a rate of 50° C./min. Melting points were collected during the heating period. The weight percent of ethylene incorporated in the ethylene-propylene copolymers was determined by rapid FT-IR spectroscopy on a Bruker Equinox 55+IR in reflection mode. Samples were prepared in a thin film format by evaporative deposition techniques. Weight percent ethylene was obtained from the ratio of peak heights at 744-715 and 1189-1126 cm-1. This method was calibrated using a set of ethylene/propylene copolymers with a range of known wt % ethylene content.

Shown in Table 1 are a series of propylene polymerizations that demonstrate that L2HfMe2, L3HfMe2, and L4HfMe2, when activated with N,N-dimethylanilium tetrakis(perfluorophenyl)borate, are capable of forming crystalline polypropylene with melting points above 120° C. Conditions: isohexane solvent, propylene added=1 mL, total volume=5 mL, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate activator (1.1 equivalent), tri-n-octylaluminum (300 nmol). Activities given in grams polymer/mmol catalyst/hour. The concentration of catalyst ranges from 0.00003 mmol to 0.00005 mmol.

Shown in Table 2, same conditions, are a series of propylene polymerizations that demonstrate the catalyst formed from L8HfMe2and N,N-dimethylanilium tetrakis(perfluorophenyl)borate is an active catalyst for propylene polymerization at 85 and 100° C. From runs 37 through 39 it is observed that polypropylene produced at 85° C. with this catalyst melts at 138-139° C. This is in between the melting points observed for polymers produced under identical conditions by the catalysts L7HfMe2(see runs 31-33) and L9HfMe2(see runs 43-45). Thus the use of pyridyldiamide ligands that contain a C8H8(xylyl) linker group between the pyridyl ring and one of the amido nitrogens is useful for controlling polymer properties, such as melting point.

TABLE 3Ethylene-octene copolymerization data. Activities given in g polymer/mmolcatalyst/hour/bar. Molecular weights are reported in g/mol.PDATyieldP[C8]wt %TmRuncomplex(° C.)(mg)(psia)(mM)activityC8MwMnPDI(° C.)49L1HfMe280327505,80701,725,35791,35818.913750L1HfMe28043750.12715,6391185,77673,9651.210751L1HfMe2105132000.12792652,95737,8831.412252L7HfMe2806775071,4000392,181258,5381.513853L7HfMe28080750.12768,46125474,642300,9771.69754L7HfMe21051172000.12723,94911668,877413,9621.610955L8HfMe28072750127,9780374,908239,3511.613756L8HfMe28099750.12774,87530432,802270,8621.69857L8HfMe2105342000.12710,1543552,372350,9421.611958L9HfMe28065750124,6330310,188222,6351.413559L9HfMe28096750.12757,62530415,923279,2071.59660L9HfMe2105672000.12735,2097494,380325,2181.5113