Polymerization of C6-C14 a-Olefin Monomers and Polymers Thereof

Abstract

The present disclosure provides a process. In an embodiment, the process includes contacting, under polymerization conditions, one or more C.sub.6-C.sub.14 α-olefin monomers with a bis-biphenylphenoxy catalyst. The process includes forming a polymer composed of one or more C.sub.6-C.sub.14 α-olefin monomers, and having an absolute weight average molecular weight (Mw.sub.(abs)) greater than 1,300,000 g/mol and a Mw.sub.(abs)/Mn.sub.(abs) from 1.3 to 3.0.

Claims

1. A process comprising: contacting, under polymerization conditions, one or more monomers consisting of C.sub.6-C.sub.14 α-olefin monomers with a bis-biphenylphenoxy catalyst; and forming a polymer composed of one or more C.sub.6-C.sub.14 α-olefin monomers, and having an absolute weight average molecular weight (Mw.sub.(abs)) greater than 1,300,000 g/mol and a Mw.sub.(abs)/Mn.sub.(abs) from 1.3 to 3.0.

2. The process of claim 1 comprising contacting one or more C.sub.6-C.sub.14 α-olefin monomers with a bis-biphenylphenoxy catalyst having the formula ##STR00011## wherein M is a metal selected from zirconium or hafnium, the metal being in a formal oxidation state of +2, +3, or +4; n is an integer of from 0 to 3, and wherein when n is 0, X is absent; and each X independently is a monodentate ligand that is neutral, monoanionic, or dianionic; or two Xs are taken together to form a bidentate ligand that is neutral, monoanionic, or dianionic; and X and n are chosen in such a way that the metal-ligand complex of formula (I) is, overall, neutral; and each Z independently is O, S, N(C.sub.1-C.sub.40)hydrocarbyl, or P(C.sub.1-C.sub.40)hydrocarbyl; and O is O (an oxygen atom); L is (C.sub.1-C.sub.40)hydrocarbylene or (C.sub.1-C.sub.40)heterohydrocarbylene, wherein the (C.sub.1-C.sub.40)hydrocarbylene has a portion that comprises a 1-carbon atom to 10-carbon atom linker backbone linking the two Z groups in formula (I) (to which L is bonded) or the (C.sub.1-C.sub.40)heterohydrocarbylene has a portion that comprises a 1-atom to 10-atom linker backbone linking the two Z groups in formula (I), wherein each of the 1 to 10 atoms of the 1-atom to 10-atom linker backbone of the (C.sub.1-C.sub.40)heterohydrocarbylene independently is a carbon atom or heteroatom, wherein each heteroatom independently is O, S, S(O), S(O).sub.2, Si(R.sup.C).sub.2, Ge(R.sup.C).sub.2, P(R.sup.C), or N(R.sup.C), wherein independently each R.sup.C is (C.sub.1-C.sub.30)hydrocarbyl or (C.sub.1-C.sub.30) heterohydrocarbyl; and each R.sup.1-16 is selected from (C.sub.1-C.sub.40)hydrocarbyl, (C.sub.1-C.sub.40)heterohydrocarbyl, Si(R.sup.C).sub.3, Ge(R.sup.C).sub.3, P(R.sup.C).sub.2, N(R.sup.C).sub.2, OR.sup.C, SR.sup.C, NO.sub.2, CN, CF.sub.3, R.sup.CS(O), R.sup.CS(O).sub.2, (R.sup.C).sub.2C═N, R.sup.CC(O)O, R.sup.COC(O), R.sup.CC(O)N(R), (R.sup.C).sub.2NC(O), halogen atom, hydrogen atom, and combinations thereof.

3. The process of claim 1 comprising contacting the one or more C.sub.6-C.sub.14 α-olefin monomers with a bis-biphenylphenoxy catalyst having the formula (V) ##STR00012## and forming a polymer composed of one or more C.sub.6-C.sub.14 α-olefin monomers and having an absolute weight average molecular weight (Mw.sub.(abs)) greater than 1,300,000 g/mol and a Mw.sub.(abs)/Mn.sub.(abs) from 1.3 to 3.0, a residual amount of zirconium, and a residual amount of germanium.

4. The process of claim 1 comprising contacting the one or more C.sub.6-C.sub.14 α-olefin monomers with a bis-biphenylphenoxy catalyst having the formula (VI) ##STR00013## and forming a polymer composed of one or more C.sub.6-C.sub.14 α-olefin monomers, and having an absolute weight average molecular weight (Mw.sub.(abs)) greater than 1,300,000 g/mol and a Mw.sub.(abs)/Mn.sub.(abs) from 1.3 to 3.0, and a residual amount of zirconium.

5. The process of claim 4 comprising contacting, under polymerization conditions, one or more C.sub.6-C.sub.8 α-olefin monomers with a bis-biphenylphenoxy catalyst having the formula (V) or the formula (VI); and forming a polymer composed of one or more C.sub.6-C.sub.8 α-olefin monomers, the polymer comprising a residual amount of zirconium and having an absolute weight average molecular weight (Mw.sub.(Abs)) greater than 1,300,000 g/mol and a Mw.sub.(Abs)/Mn.sub.(Abs) from 1.3 to 3.0.

6. The process of claim 5 comprising contacting, under polymerization conditions, octene monomer with a bis-biphenylphenoxy catalyst having the formula (V) or the formula (VI); and forming an octene homopolymer comprising a residual amount of zirconium and having an absolute weight average molecular weight (Mw.sub.(Abs)) greater than 1,300,000 g/mol and a Mw.sub.(Abs)/Mn.sub.(Abs) from 1.3 to 3.0.

7. The process of claim 6 comprising contacting, under polymerization conditions, octene monomer with a bis-biphenylphenoxy catalyst having the formula (V); and forming an octene homopolymer comprising a residual amount of germanium and having an absolute weight average molecular weight (Mw.sub.(Abs)) greater than 1,300,000 g/mol and a Mw.sub.(Abs)/Mn.sub.(Abs) from 1.3 to 3.0.

8. A composition comprising: a polymer consisting of one or more C.sub.6-C.sub.14 α-olefin monomers, the polymer comprising boron; and a residual amount of zirconium, the polymer having an absolute weight average molecular weight (Mw.sub.(Abs)) greater than 1,300,000 g/mol and a Mw.sub.(Abs)/Mn.sub.(Abs) from 1.3 to 3.0.

9. The composition of claim 8 wherein the polymer comprises ppm titanium.

10. The composition of claim 8 wherein the polymer comprises from greater than 0 ppm to 300 ppm zirconium.

11. The composition of claim 8 wherein the polymer comprises from greater than 0 ppm to 300 ppm germanium.

12. The composition of claim 8 wherein the polymer is selected from the group consisting of octene homopolymer and hexene homopolymer.

13. The process of claim 1 wherein the contacting occurs at a temperature from 23° C. to 25° C.

14. The process of claim 13 comprising contacting the one or more C.sub.6-C.sub.14 α-olefin monomers with the bis-biphenylphenoxy catalyst and a boron-containing co-catalyst.

15. The composition of claim 8 wherein the polymer comprises a bis-biphenylphenoxy metal-ligand complex having the formula (I) ##STR00014## wherein M is zirconium; n is an integer of from 0 to 3, and wherein when n is 0, X is absent; and each X independently is a monodentate ligand that is neutral, monoanionic, or dianionic; or two Xs are taken together to form a bidentate ligand that is neutral, monoanionic, or dianionic; and X and n are chosen in such a way that the metal-ligand complex of formula (I) is, overall, neutral; and each Z independently is O, S, N(C.sub.1-C.sub.40)hydrocarbyl, or P(C.sub.1-C.sub.40)hydrocarbyl; and O is O (an oxygen atom); L is (C.sub.1-C.sub.40)hydrocarbylene or (C.sub.1-C.sub.40)heterohydrocarbylene, wherein the (C.sub.1-C.sub.40)hydrocarbylene has a portion that comprises a 1-carbon atom to 10-carbon atom linker backbone linking the two Z groups in formula (I) (to which L is bonded) or the (C.sub.1-C.sub.40)heterohydrocarbylene has a portion that comprises a 1-atom to 10-atom linker backbone linking the two Z groups in formula (I), wherein each of the 1 to 10 atoms of the 1-atom to 10-atom linker backbone of the (C.sub.1-C.sub.40)heterohydrocarbylene independently is a carbon atom or heteroatom, wherein each heteroatom independently is O, S, S(O), S(O).sub.2, Si(R.sup.C).sub.2, Ge(R.sup.C).sub.2, P(R.sup.C), or N(R.sup.C), wherein independently each R.sup.C is (C.sub.1-C.sub.30)hydrocarbyl or (C.sub.1-C.sub.30) heterohydrocarbyl; and each R.sup.1-16 is selected from (C.sub.1-C.sub.40)hydrocarbyl, (C.sub.1-C.sub.40)heterohydrocarbyl, Si(R.sup.C).sub.3, Ge(R.sup.C).sub.3, P(R.sup.C).sub.2, N(R.sup.C).sub.2, OR.sup.C, SR.sup.C, NO.sub.2, CN, CF.sub.3, R.sup.CS(O), R.sup.CS(O).sub.2, (R.sup.C).sub.2C═N, R.sup.CC(O)O, R.sup.COC(O), R.sup.CC(O)N(R), (R.sup.C).sub.2NC(O), halogen atom, hydrogen atom, and combinations thereof.

Description

DETAILED DESCRIPTION

[0032] The present disclosure provides a process. In an embodiment, the process includes contacting, under polymerization conditions, one or more C.sub.6-C.sub.14 α-olefin monomers with a bis-biphenylphenoxy catalyst. The process includes forming a polymer composed of one or more C.sub.6-C.sub.14 α-olefin monomers, the polymer having an absolute weight average molecular weight (Mw.sub.(Abs)) greater than 1,300,000 g/mol and a Mw.sub.(Abs)/Mn.sub.(Abs) from 1.3 to 3.0.

[0033] The process includes contacting, under polymerization conditions, one or more C.sub.6-C.sub.14 α-olefin monomers with a bis-biphenylphenoxy catalyst. As used herein, “polymerization conditions,” are temperature, pressure, reactant concentrations, solvent selection, chain transfer agent (CTA), reactant mixing/addition parameters, and other conditions within a polymerization reactor that promote reaction between the reagents and formation of the resultant product, namely a polymer composed of one or more C.sub.6-C.sub.14 α-olefin monomers. Polymerization may be conducted in a tubular reactor, in a stirred autoclave, a continuous stirred tank reactor, a gas phase polymerization reactor, a slurry phase polymerization reactor, a loop reactor, an isothermal reactor, a fluidized bed gas phase reactor and combinations thereof in a batch process or a continuous process.

[0034] Under polymerization conditions, the one or more C.sub.6-C.sub.14 α-olefin monomers are contacted with a bis-biphenylphenoxy catalyst (or interchangeably referred to as “BBP”). The bis-biphenylphenoxy catalyst is a metal-ligand complex with a structure as shown in formula (I) below:

##STR00003##

[0035] wherein

[0036] M is a metal selected from zirconium or hafnium, the metal being in a formal oxidation state of +2, +3, or +4;

[0037] n is an integer of from 0 to 3, and wherein when n is 0, X is absent; and

[0038] each X independently is a monodentate ligand that is neutral, monoanionic, or dianionic; or two Xs are taken together to form a bidentate ligand that is neutral, monoanionic, or dianionic; and X and n are chosen in such a way that the metal-ligand complex of formula (I) is, overall, neutral; and

[0039] each Z independently is O, S, N(C.sub.1-C.sub.40)hydrocarbyl, or P(C.sub.1-C.sub.40)hydrocarbyl; and

[0040] O is O (an oxygen atom);

[0041] L is (C.sub.1-C.sub.40)hydrocarbylene or (C.sub.1-C.sub.40)heterohydrocarbylene, wherein the (C.sub.1-C.sub.40)hydrocarbylene has a portion that comprises a 1-carbon atom to 10-carbon atom linker backbone linking the two Z groups in formula (I) (to which L is bonded) or the (C.sub.1-C.sub.40)heterohydrocarbylene has a portion that comprises a 1-atom to 10-atom linker backbone linking the two Z groups in formula (I), wherein each of the 1 to 10 atoms of the 1-atom to 10-atom linker backbone of the (C.sub.1-C.sub.40)heterohydrocarbylene independently is a carbon atom or heteroatom, wherein each heteroatom independently is O, S, S(O), S(O).sub.2, Si(R.sup.C).sub.2, Ge(R.sup.C).sub.2, P(R.sup.C), or N(R.sup.C), wherein independently each R.sup.C is (C.sub.1-C.sub.30)hydrocarbyl or (C.sub.1-C.sub.30) heterohydrocarbyl; and

[0042] each R.sup.1-16 is selected from (C.sub.1-C.sub.40)hydrocarbyl, (C.sub.1-C.sub.40)heterohydrocarbyl, Si(R.sup.C).sub.3, Ge(R.sup.C).sub.3, P(R.sup.C).sub.2, N(R.sup.C).sub.2, OR.sup.C, SR.sup.C, NO.sub.2, CN, CF.sub.3, R.sup.CS(O), R.sup.CS(O).sub.2, (R.sup.C).sub.2C═N, R.sup.CC(O)O, R.sup.COC(O), R.sup.CC(O)N(R), (R.sup.C).sub.2NC(O), halogen atom, hydrogen atom, and combinations thereof.

[0043] The bis-biphenylphenoxy catalyst with structure of formula (I) may be rendered catalytically active by contacting the metal-ligand complex to, or combining the metal-ligand complex with, an activating co-catalyst.

[0044] Nonlimiting examples of suitable activating co-catalysts for use herein include alkyl aluminums; polymeric or oligomeric alumoxanes (also known as aluminoxanes); neutral Lewis acids; and non-polymeric, non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions). Combinations of one or more of the foregoing activating co-catalysts and techniques are also contemplated. The term“alkyl aluminum” means a monoalkyl aluminum dihydride or monoalkylaluminum dihalide, a dialkyl aluminum hydride or dialkyl aluminum halide, or a trialkylaluminum. Examples of polymeric or oligomeric alumoxanes include methylalumoxane, triisobutylaluminum-modified methylalumoxane, and isobutylalumoxane.

[0045] Nonlimiting examples of suitable Lewis acid activators (co-catalysts) include Group 13 metal compounds containing from 1 to 3 (C.sub.1-C.sub.20)hydrocarbyl substituents as described herein. In one embodiment, Group 13 metal compounds are tri((C.sub.1-C.sub.20)hydrocarbyl)-substituted-aluminum, tri((C.sub.1-C.sub.20)hydrocarbyl)-boron compounds, tri((C.sub.1-C.sub.10)alkyl)aluminum, tri((C.sub.6-C.sub.18)aryl)boron compounds, and halogenated (including perhalogenated) derivatives thereof. In further embodiments, Group 13 metal compounds are tris(fluoro-substituted phenyl)boranes, tris(pentafluorophenyl)borane. In some embodiments, the activating co-catalyst is a tetrakis((C.sub.1-C.sub.20)hydrocarbyl borate or a tri((C.sub.1-C.sub.20)hydrocarbyl)ammonium tetrakis((C.sub.1-C.sub.20)hydrocarbyl)borate (e.g. bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borate). As used herein, the term “ammonium” means a nitrogen cation that is a ((C.sub.1-C.sub.20)hydrocarbylN(H).sub.3.sup.+, or N(H).sub.4.sup.+, wherein each (C.sub.1-C.sub.20)hydrocarbyl, when two or more are present, may be the same or different.

[0046] Nonlimiting examples of combinations of neutral Lewis acid activators (co-catalysts) include mixtures comprising a combination of a tri((C.sub.1-C.sub.4)alkyl)aluminum and a halogenated tri((C.sub.6-C.sub.13)aryl)boron compound, especially a tris(pentafluorophenyl)borane. Other embodiments are combinations of such neutral Lewis acid mixtures with a polymeric or oligomeric alumoxane, and combinations of a single neutral Lewis acid, especially tris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxane. Ratios of numbers of moles of (metal-ligand complex):(tris(pentafluoro-phenylborane):(alumoxane) [e.g., (Group 4 metal-ligand complex):(tris(pentafluoro-phenylborane):(alumoxane)] are from 1:1:1 to 1:10:100, in other embodiments, from 1:1:1.5 to 1:5:30.

[0047] The bis-biphenylphenoxy catalyst with structure of formula (I) may be activated to form an active catalyst composition by combination with one or more co-catalysts, for example, a cation forming co-catalyst, a strong Lewis acid, or combinations thereof. Suitable activating co-catalysts include polymeric or oligomeric aluminoxanes, especially methyl aluminoxane, as well as inert, compatible, noncoordinating, ion forming compounds. Exemplary suitable co-catalysts include, but are not limited to: modified methyl aluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl tetrakis(pentafluorophenyl)borate(1<->) amine (i.e. [HNMe(C.sub.18H.sub.37).sub.2][B(C.sub.6F.sub.5).sub.4]), and combinations of both.

[0048] One or more of the foregoing activating co-catalysts are used in combination with each other. In an embodiment, the co-catalyst is a mixture of a tri((C.sub.1-C.sub.4)hydrocarbyl)aluminum, tri((C.sub.1-C.sub.4)hydrocarbyl)borane, or an ammonium borate with an oligomeric or polymeric alumoxane compound. The ratio of total number of moles of one or more metal-ligand complexes of formula (I) to total number of moles of one or more of the activating co-catalysts is from 1:10,000 to 100:1. In some embodiments, the ratio is at least 1:5000, in some other embodiments, at least 1:1000; and 10:1 or less, and in some other embodiments, 1:1 or less. When an alumoxane alone is used as the activating co-catalyst, preferably the number of moles of the alumoxane that are employed is at least 100 times the number of moles of the metal-ligand complex of formula (I). When tris(pentafluorophenyl)borane alone is used as the activating co-catalyst, in some other embodiments, the number of moles of the tris(pentafluorophenyl)borane that are employed to the total number of moles of one or more metal-ligand complexes of formula (I) from 0.5:1 to 10:1, from 1:1 to 6:1, or from 1:1 to 5:1. The remaining activating co-catalysts are generally employed in approximately mole quantities equal to the total mole quantities of one or more metal-ligand complexes of formula (I).

[0049] In an embodiment, the bis-biphenylphenoxy catalyst with structure of formula (I) includes the metal M that is zirconium.

[0050] The process includes contacting the one or more C.sub.6-C.sub.14 α-olefin monomers under polymerization conditions with the bis-biphenylphenoxy catalyst of formula (I), and forming a polymer composed of one or more C.sub.6-C.sub.14 α-olefin monomers. The polymer can be a homopolymer of one monomer selected from C.sub.6-C.sub.14 α-olefin (hereafter “a C.sub.6-C.sub.14 α-olefin homopolymer”), a copolymer with two monomers selected from C.sub.6-C.sub.14 α-olefin (hereafter “a C.sub.6-C.sub.14 α-olefin copolymer”), or a terpolymer with three monomers selected from C.sub.6-C.sub.14 α-olefin (hereafter “a C.sub.6-C.sub.14 α-olefin terpolymer”). The polymer (i.e., the C.sub.6-C.sub.14 α-olefin homopolymer, the C.sub.6-C.sub.14 α-olefin copolymer, or the C.sub.6-C.sub.14 α-olefin terpolymer) has an absolute weight average molecular weight (Mw.sub.(Abs)) greater than 1,300,000 g/mol and a Mw.sub.(Abs)/Mn.sub.(Abs) from 1.3 to 3.0.

[0051] The polymer (i.e., the C.sub.6-C.sub.14 α-olefin homopolymer, the C.sub.6-C.sub.14 α-olefin copolymer, or the C.sub.6-C.sub.14 α-olefin terpolymer) includes a residual amount of zirconium, or hafnium or from greater than 0 ppm to 300 ppm zirconium and contains little, or no, titanium or from 0 ppm to less than 10 ppm titanium.

[0052] In an embodiment, the bis-biphenylphenoxy catalyst is a metal-ligand complex having the structure formula (V) below:

##STR00004##

[0053] wherein Ge is germanium, Me is a methyl group, tBu is a t-butyl group, and iPr is an isopropyl group. The process includes contacting the one or more C.sub.6-C.sub.14 α-olefin monomers under polymerization conditions with the bis-biphenylphenoxy catalyst of formula (V), and forming a polymer (i.e., a C.sub.6-C.sub.14 α-olefin homopolymer, a C.sub.6-C.sub.14 α-olefin copolymer, or a C.sub.6-C.sub.14 α-olefin terpolymer). The polymer (i.e., the C.sub.6-C.sub.14 α-olefin homopolymer, the C.sub.6-C.sub.14 α-olefin copolymer, or the C.sub.6-C.sub.14 α-olefin terpolymer) has one, some, or all of the following properties:

[0054] (i) a Mw.sub.(Abs) from greater than 1,300,000 g/mol to 12,000,000 g/mol, or from 1,400,000 g/mol to 10,000,000 g/mol, or from 1,400,000 g/mol to 9,000,000 g/mol, or from 1,500,000 g/mol to 8,000,000 g/mol; and/or

[0055] (ii) Mw.sub.(Abs)/Mn.sub.(Abs) from 1.3 to 3.0, or from 1.4 to 2.9, or from 1.5 to 2.8, or from 2.1 to 2.7, or from 2.2 to 2.6; and/or

[0056] (iii) a residual amount of germanium, or from greater than 0 ppm, or 1 ppm to less than 300 ppm, or from 10 ppm to 200 ppm, or from 12 ppm to 150 ppm, or from 14 ppm to 130 ppm, or from 14 ppm to 125 ppm germanium; and/or

[0057] (iv) a residual amount of zirconium, or from greater than 0 ppm, or 1 ppm to less than 300 ppm, or from 10 ppm to 200 ppm, or from 15 ppm to 180 ppm, or from 20 ppm to 170 ppm, or from 30 ppm to 160 ppm zirconium.

[0058] In an embodiment, the bis-biphenylphenoxy catalyst is a metal-ligand complex having the structure formula (VI) below:

##STR00005##

[0059] wherein Me is a methyl group, and tBu is a t-butyl group. The process includes contacting the one or more C.sub.6-C.sub.14 α-olefin monomers under polymerization conditions with the bis-biphenylphenoxy catalyst of formula (VI), and forming an octene polymer having one, some, or all of the following properties:

[0060] (i) a Mw.sub.(Abs) from greater than 1,300,000 g/mol to 12,000,000 g/mol, or from 1,400,000 g/mol to 10,000,000 g/mol, or from 1,400,000 g/mol to 9,000,000 g/mol, or from 1,500,000 g/mol to 8,000,000 g/mol; and/or

[0061] (ii) Mw.sub.(Abs)/Mn.sub.(Abs) from 1.3 to 3.0, or from 1.4 to 2.9, or from 1.5 to 2.8, or from 2.1 to 2.7, or from 2.2 to 2.6; and/or

[0062] (iii) a residual amount of zirconium, or from greater than 0 ppm, or 1 ppm to less than 300 ppm, or from 10 ppm to 200 ppm, or from 15 ppm to 180 ppm, or from 20 ppm to 170 ppm, or from 30 ppm to 160 ppm zirconium (hereafter Polymer1).

[0063] In an embodiment, the zirconium is present in the polymer composed of one or more C.sub.6-C.sub.14 α-olefins (Polymer1) to the exclusion of titanium and/or to the exclusion of hafnium.

[0064] In an embodiment, the process includes contacting, under polymerization conditions, one or more C.sub.6-C.sub.8 α-olefin monomers with the bis-biphenylphenoxy catalyst having the formula (I) or formula (V), or formula (VI). The process includes forming a polymer composed of one or more C.sub.6-C.sub.8 α-olefin monomers. The polymer composed of one or more C.sub.6-C.sub.8 α-olefin monomers is a hexene homopolymer, a heptene homopolymer, an octene homopolymer, a hexene/heptene copolymer, a hexene/octene copolymer, a heptene/octene copolymer, or a hexene/heptene/octene terpolymer. The polymer composed of one or more C.sub.6-C.sub.8 α-olefin monomers has one, some, or all of the following properties:

[0065] (i) a Mw.sub.(Abs) from greater than 1,300,000 g/mol to 12,000,000 g/mol, or from 1,400,000 g/mol to 10,000,000 g/mol, or from 1,400,000 g/mol to 9,000,000 g/mol, or from 1,500,000 g/mol to 8,000,000 g/mol; and/or

[0066] (ii) Mw.sub.(Abs)/Mn.sub.(Abs) from 1.3 to 3.0, or from 1.4 to 2.9, or from 1.5 to 2.8, or from 2.1 to 2.7, or from 2.2 to 2.6; and/or

[0067] (iii) a residual amount of germanium, or from greater than 0 ppm, or 1 ppm to less than 300 ppm, or from 10 ppm to 200 ppm, or from 12 ppm to 150 ppm, or from 14 ppm to 130 ppm, or from 14 ppm to 125 ppm germanium; and/or

[0068] (iv) a residual amount of zirconium, or from greater than 0 ppm, or 1 ppm to less than 300 ppm, or from 10 ppm to 200 ppm, or from 15 ppm to 180 ppm, or from 20 ppm to 170 ppm, or from 30 ppm to 160 ppm zirconium (hereafter Polymer2).

[0069] In an embodiment, the zirconium and/or the germanium is present in the polymer composed of one or more C.sub.6-C.sub.8 α-olefins (Polymer2) to the exclusion of titanium. In a further embodiment, the polymer composed of one or more C.sub.6-C.sub.8 α-olefin monomers (Polymer2) contains a residual amount of zirconium (and optionally a residual amount of germanium) and further contains from 0 ppm to less than 10 ppm titanium.

[0070] In an embodiment, the process includes contacting, under polymerization conditions, octene monomer with the bis-biphenylphenoxy catalyst having the formula (I) or formula (V), or formula (VI). The process includes forming an octene homopolymer. The octene homopolymer has one, some, or all of the following properties:

[0071] (i) a Mw.sub.(Abs) from greater than 1,300,000 g/mol to 12,000,000 g/mol, or from 1,400,000 g/mol to 10,000,000 g/mol, or from 1,400,000 g/mol to 9,000,000 g/mol, or from 1,500,000 g/mol to 8,000,000 g/mol; and/or

[0072] (ii) Mw.sub.(Abs)/Mn.sub.(Abs) from 1.3 to 3.0, or from 1.4 to 2.9, or from 1.5 to 2.8, or from 2.1 to 2.7, or from 2.2 to 2.6; and/or

[0073] (iii) a residual amount of germanium, or from greater than 0 ppm, or 1 ppm to less than 300 ppm, or from 10 ppm to 200 ppm, or from 12 ppm to 150 ppm, or from 14 ppm to 130 ppm, or from 14 ppm to 125 ppm germanium; and/or

[0074] (iv) a residual amount of zirconium, or from greater than 0 ppm, or 1 ppm to less than 300 ppm, or from 10 ppm to 200 ppm, or from 15 ppm to 180 ppm, or from 20 ppm to 170 ppm, or from 30 ppm to 160 ppm zirconium (hereafter Polymer3).

[0075] In an embodiment, the zirconium and/or the germanium is present in the octene homopolymer (Polymer3) to the exclusion of titanium, or from 0 ppm to less than 10 ppm titanium.

[0076] In an embodiment, the process includes contacting, under polymerization conditions, hexene monomer with the bis-biphenylphenoxy catalyst having the formula (I) of formula (V), or formula (VI). The process includes forming a hexene homopolymer. The hexene homopolymer has one, some, or all of the following properties:

[0077] (i) a Mw.sub.(Abs) from greater than 1,300,000 g/mol to 12,000,000 g/mol, or from 1,400,000 g/mol to 10,000,000 g/mol, or from 1,400,000 g/mol to 9,000,000 g/mol, or from 1,500,000 g/mol to 8,000,000 g/mol; and/or

[0078] (ii) Mw.sub.(Abs)/Mn.sub.(Abs) from 1.3 to 3.0, or from 1.4 to 2.9, or from 1.5 to 2.8, or from 2.1 to 2.7, or from 2.2 to 2.6; and/or

[0079] (iii) a residual amount of germanium, or from greater 0 ppm, or than 1 ppm to less than 300 ppm, or from 10 ppm to 200 ppm, or from 12 ppm to 150 ppm, or from 14 ppm to 130 ppm, or from 14 ppm to 125 ppm germanium; and/or

[0080] (iv) a residual amount of zirconium, or from greater than 0 ppm, or 1 ppm to less than 300 ppm, or from 10 ppm to 200 ppm, or from 15 ppm to 180 ppm, or from 20 ppm to 170 ppm, or from 30 ppm to 160 ppm zirconium (hereafter Polymer4).

[0081] In an embodiment, the germanium and/or the zirconium is present in the hexene homopolymer (Polymer4) to the exclusion of titanium, or from 0 ppm to less than 10 ppm titanium.

[0082] 2. Composition

[0083] The present disclosure provides a composition. In an embodiment, the composition includes a polymer composed of one or more C.sub.6-C.sub.14 α-olefin monomers (i.e., the C.sub.6-C.sub.14 α-olefin homopolymer, the C.sub.6-C.sub.14 α-olefin copolymer, or the C.sub.6-C.sub.14 α-olefin terpolymer). The polymer composed of one or more C.sub.6-C.sub.14 α-olefin monomers has one, some, or all of the following properties:

[0084] (i) a Mw.sub.(Abs) from greater than 1,300,000 g/mol to 12,000,000 g/mol, or from 1,400,000 g/mol to 10,000,000 g/mol, or from 1,400,000 g/mol to 9,000,000 g/mol, or from 1,500,000 g/mol to 8,000,000 g/mol; and/or

[0085] (ii) Mw.sub.(Abs)/Mn.sub.(Abs) from 1.3 to 3.0, or from 1.4 to 2.9, or from 1.5 to 2.8, or from 2.1 to 2.7, or from 2.2 to 2.6; and/or

[0086] (iii) a residual amount of germanium, or from greater than 0 ppm, or 1 ppm to less than 300 ppm, or from 10 ppm to 200 ppm, or from 12 ppm to 150 ppm, or from 14 ppm to 130 ppm, or from 14 ppm to 125 ppm germanium; and/or

[0087] (iv) a residual amount of zirconium, or from greater than 0 ppm, or 1 ppm to less than 300 ppm, or from 10 ppm to 200 ppm, or from 15 ppm to 180 ppm, or from 20 ppm to 170 ppm, or from 30 ppm to 160 ppm zirconium (Polymer1).

[0088] In an embodiment, the germanium and/or the zirconium is present in the polymer composed of one or more C.sub.6-C.sub.14 α-olefins (Polymer1) to the exclusion of titanium and/or to the exclusion of hafnium. In a further embodiment, the polymer composed of one or more C.sub.6-C.sub.14 α-olefins (Polymer1) contains a residual amount of zirconium (and optionally a residual amount of germanium) and from 0 ppm to less than 10 ppm titanium.

[0089] In an embodiment the composition includes a polymer composed of one or more C.sub.6-C.sub.8 α-olefin monomers. The polymer composed of one or more C.sub.6-C.sub.8 α-olefin monomers is a hexene homopolymer, a heptene homopolymer, an octene homopolymer, a hexene/heptene copolymer, a hexene/octene copolymer, a heptene/octene copolymer, or a hexene/heptene/octene terpolymer. The polymer composed of one or more C.sub.6-C.sub.8 α-olefin monomers contains a residual amount of germanium and has one, some, or all of the following properties:

[0090] (i) a Mw.sub.(Abs) from greater than 1,300,000 g/mol to 12,000,000 g/mol, or from 1,400,000 g/mol to 10,000,000 g/mol, or from 1,400,000 g/mol to 9,000,000 g/mol, or from 1,500,000 g/mol to 8,000,000 g/mol; and/or

[0091] (ii) Mw.sub.(Abs)/Mn.sub.(Abs) from 1.3 to 3.0, or from 1.4 to 2.9, or from 1.5 to 2.8, or from 2.1 to 2.7, or from 2.2 to 2.6; and/or

[0092] (iii) a residual amount of germanium, or from greater than 0 ppm, or 1 ppm to less than 300 ppm, or from 10 ppm to 200 ppm, or from 12 ppm to 150 ppm, or from 14 ppm to 130 ppm, or from 14 ppm to 125 ppm germanium; and/or

[0093] (iv) a residual amount of zirconium, or from greater than 0 ppm, or 1 ppm to less than 300 ppm, or from 10 ppm to 200 ppm, or from 15 ppm to 180 ppm, or from 20 ppm to 170 ppm, or from 30 ppm to 160 ppm zirconium (Polymer2).

[0094] In an embodiment, the germanium and/or the zirconium is present in the polymer composed of one or more C.sub.6-C.sub.8 α-olefins (Polymer2) to the exclusion of titanium and/or to the exclusion of hafnium. In a further embodiment, the polymer composed of one or more C.sub.6-C.sub.8 α-olefins (Polymer2) contains a residual amount of zirconium (and optionally a residual amount of germanium) and from 0 ppm to less than 10 ppm titanium.

[0095] In an embodiment, the composition includes an octene homopolymer. The octene homopolymer has one, some, or all of the following properties:

[0096] (i) a Mw.sub.(Abs) from greater than 1,300,000 g/mol to 12,000,000 g/mol, or from 1,400,000 g/mol to 10,000,000 g/mol, or from 1,400,000 g/mol to 9,000,000 g/mol, or from 1,500,000 g/mol to 8,000,000 g/mol; and/or

[0097] (ii) Mw.sub.(Abs)/Mn.sub.(Abs) from 1.3 to 3.0, or from 1.4 to 2.9, or from 1.5 to 2.8, or from 2.1 to 2.7, or from 2.2 to 2.6; and/or

[0098] (iii) a residual amount of germanium, or from greater than 0 ppm, or 1 ppm to less than 300 ppm, or from 10 ppm to 200 ppm, or from 12 ppm to 150 ppm, or from 14 ppm to 130 ppm, or from 14 ppm to 125 ppm germanium; and/or

[0099] (iv) a residual amount of zirconium, or from greater than 0 ppm, or 1 ppm to less than 300 ppm, or from 10 ppm to 200 ppm, or from 15 ppm to 180 ppm, or from 20 ppm to 170 ppm, or from 30 ppm to 160 ppm zirconium (Polymer3).

[0100] In an embodiment, the zirconium is present in the octene homopolymer (Polymer3) to the exclusion of titanium. In a further embodiment, the octene homopolymer (Polymer3) contains a residual amount of zirconium (and optionally a residual amount of germanium and from 0 ppm to less than 10 ppm titanium.

[0101] In an embodiment, the composition includes a hexene homopolymer. The hexene homopolymer has one, some, or all of the following properties:

[0102] (i) a Mw.sub.(Abs) from greater than 1,300,000 g/mol to 12,000,000 g/mol, or from 1,400,000 g/mol to 10,000,000 g/mol, or from 1,400,000 g/mol to 9,000,000 g/mol, or from 1,500,000 g/mol to 8,000,000 g/mol; and/or

[0103] (ii) Mw.sub.(Abs)/Mn.sub.(Abs) from 1.3 to 3.0, or from 1.4 to 2.9, or from 1.5 to 2.8, or from 2.1 to 2.7, or from 2.2 to 2.6; and/or

[0104] (iii) a residual amount of germanium, or from greater than 0 ppm, or 1 ppm to less than 300 ppm, or from 10 ppm to 200 ppm, or from 12 ppm to 150 ppm, or from 14 ppm to 130 ppm, or from 14 ppm to 125 ppm germanium; and/or

[0105] (iv) a residual amount of zirconium, or from greater than 0 ppm, or 1 ppm to less than 300 ppm, or from 10 ppm to 200 ppm, or from 15 ppm to 180 ppm, or from 20 ppm to 170 ppm, or from 30 ppm to 160 ppm zirconium (Polymer4).

[0106] In an embodiment, the zirconium is present in the hexene homopolymer (Polymer4) to the exclusion of titanium. In a further embodiment, the hexene homopolymer (Polymer4) contains a residual amount of zirconium (and optionally a residual amount of germanium) and from 0 ppm to less than 10 ppm titanium.

[0107] By way of example, and not limitation, some embodiments of the present disclosure will now be described in detail in the following Examples.

Examples

[0108] The catalysts used in the comparative samples (CS) are provided in Table 1 below. Catalysts used in the inventive examples (IE) are provided in Table 2 below.

TABLE-US-00001 TABLE 1 Catalysts used to produce comparative samples Comparative Catalysts Chemical formula Ziegler-Natta Catalyst BuEtMg, MgCl.sub.2, Ti(O/Pr).sub.4 (ZN) 3 Ti: 40 Mg: 12 Al Constrained geometry Catalyst (CGC) [00006] Titanium, [N-(1,1-dimethylethyl)-1,1-dimethyl-1-[(1,2,3,3a,8a-.eta.)-1,5,6,7-tetrahydro-2- methyl-s-indacen-1-yl]silanaminato(2-)-.kappa.N][(1,2,3,4-.eta.)-1,3-pentadiene]-, stereoisomer CAS 199876-48-7; CAS 200074-30-2 Metallocene catalyst 1 (Metallocene 1) [00007] rac-dimethylsilyl-bis-(2-methyl-4-phenyl-n5-indenyl) zirconium (n4-trans-trans-1,4 diphenyl- 1,3-butadiene) Metallocene catalyst 2 (Metallocene 2) [00008] rac-dimethylsilyl-bis-(2-methyl-4-phenyl-n5-indenyl) zirconium dichloride

TABLE-US-00002 TABLE 2 Catalysts used to produce inventive examples Inventive catalysts Chemical formula BBP1 Bis-biphenylphenoxy catalyst (BBP1) formula (V) [00009] Zirconium, [[2,2′′′-[[bis[l-methylethyl)germylene]bis(methyleneoxy-.kappa.O)]bis[3″,5,5″- tris(1,1-dimethylethyl)-5′-octyl[1,1′:3′,l″-terphenyl]-2′-olato-κO]](2-)]dimethyl- CAS 958647-88-6 BBP2 Bis-biphenylphenoxy catalyst (BBP 2) [00010] Zirconium, dimethyl[[2,2′′′-[1,3-propanediylbis(oxy-κO)]bis[3″,5,5″-tris(1,1-dimethylethyl)-5′- methyl[1,1′:3′,1″-terphenyl]-2′-olato-κO]](2-)]-, CAS 958647-88-6; CAS 1001417-33-9
A. Polymerization of 1-hexene and 1-octene

[0109] For comparative sample 1 (CS1), polymerization is conducted with a Ziegler-Natta Catalyst (ZN), in a 40 mL vial charged with 4 mL 1-octene and 8 mL solvent (Isopar E), 4 μmol catalyst (ZN), and 5 eq. of Et.sub.3Al (as an activator), for a period of twelve hours and at a temperature of 23-25° C. Then, solvent is removed under a vacuum.

[0110] For comparative sample 2 (CS2), polymerization is conducted with a CGC Catalyst (as shown in Table 1), in a 40 mL vial charged 4 mL 1-octene and 8 mL solvent (Isopar E), 4 μmol catalyst, 1.2 eq RIBS-2, for a period of twelve hours and at a temperature of 23-25° C. Then, solvent is removed under a vacuum

[0111] For comparative sample 3 (CS3), polymerization is conducted with a metallocene 1 catalyst (as shown in Table 1), in a 40 mL vial charged 6 mL 1-octene and 12 mL solvent (Isopar E), 2 μmol catalyst, 1.2 eq RIBS-2, 10 eq MMAO 3A, for a period of twelve hours and at a temperature of 23-25° C. Then, solvent and unreacted octene isomers are removed under a vacuum.

[0112] For comparative sample 4 (CS4), polymerization is conducted with a metallocene 2 catalyst (as shown in Table 1), in a 40 mL vial charged 6 mL 1-octene and with 12 mL solvent (Isopar E), 2 μmol catalyst, 1.2 eq RIBS-2, 10 eq MMAO 3A for a period of twelve hours and at a temperature of 23-25° C. Then, solvent and unreacted octene isomers are removed under a vacuum.

[0113] For inventive examples 1-4 (IE1-4), polymerization is conducted with a bis-biphenylphenoxy catalyst (BBP1) in a 40 mL vial charged with 8 mL 1-octene and 12 mL Isopar-E (in Isopar E), 4 μmol catalyst, and 1.2 eq. RIBS-2 (R.sub.2N(H)Me B(C.sub.6F.sub.5).sub.4, wherein R is hydrogenated tallowalkyl (C.sub.14-18 alkyl)(CAS number 200644-82-2) as an activator), for a period of twelve hours and at a temperature of 23-25° C. Then, solvent is removed under a vacuum.

[0114] For inventive example 5 (IE5), polymerization is conducted with a bis-biphenylphenoxy catalyst (BBP1) in a 40 mL vial charged with 8 mL 1-hexene and 12 mL Isopar-E, 4 μmol catalyst, and 1.2 eq. RIBS-2 (R.sub.2N(H)Me B(C.sub.6F.sub.5).sub.4, wherein R is hydrogenated tallowalkyl (C.sub.14-18 alkyl)(CAS number 200644-82-2) as an activator), for a period of twelve hours and at a temperature of 23-25° C. Then, solvent and unreacted hexene isomers are removed under a vacuum.

[0115] For inventive examples 6-7 (IE6-7), polymerization is conducted with a bis-biphenylphenoxy catalyst (BBP2) in a 40 mL vial charged with 8 mL 1-octene and 12 mL Isopar-E (in Isopar E), 4 μmol catalyst, and 1.2 eq. RIBS-2 (R.sub.2N(H)Me B(C.sub.6F.sub.5).sub.4, wherein R is hydrogenated tallowalkyl (C.sub.14-18 alkyl)(CAS number 200644-82-2) as an activator), for a period of twelve hours and at a temperature of 23-25° C. Then, solvent and unreacted octene isomers are removed under a vacuum.

[0116] The properties of the resulting octene homopolymers (and hexene homopolymer) are provided in Table 3 below.

TABLE-US-00003 TABLE 3 Polymer properties Mw Residual Polymerization Mw (Abs) Mn (Abs) (Abs)/Mn Catalyst Residual Sample Monomer Catalyst (g/mol) (g/mol) (Abs) Metal.sup.1 Germanium.sup.1 CS1 1-Octene in ZN 1,246,812 150,153 8.30 77 ppm Ti — Isopar E CS2 1-Octene in CGC 52,836 21,558 2.45 78 ppm Ti — Isopar E CS3 1-Octene in Metallocene 1 158,646 79,481 2.00 46 ppm Zr — Isopar E CS4 1-Octene in Metallocene 2 93,603 46,021 2.03 42 ppm Zr — Isopar E IE1 1-Octene in BBP1 1,739,387 1,134,761 1.53 155 ppm Zr 123 ppm Ge Isopar E IE2 1-Octene in BBP1 3,713,110 1,892,694 1.96 64 ppm Zr 51 ppm Ge Isopar-E IE3 1-Octene in BBP1 4,774,694 2,963,171 1.61 43 ppm Zr 34 ppm Ge Isopar-E IE4 1-Octene in BBP1 6,452,334 3,453,915 1.87 54 ppm Zr 43 ppm Ge Isopar-E IE5 1-Hexene in BBP1 1,748,106 1,122,559 1.56 90 ppm Zr 72 ppm Ge Isopar-E IE6 1-octene in BBP 2 1,674,376 944,359 1.77 40 ppm Zr — Isopar-E and octene isomers IE7 1-octene in BBP 2 2,243,290 1,070,812 2.09 44 ppm Zr — Isopar-E and octene isomers .sup.1ppm residual catalyst metal present in homopolymer, based on the total weight of the homopolymer

[0117] Table 3 shows that surprisingly polymerization with BBP catalysts (BBP 1 or BBP 2) resulted in high molecular weight octene homopolymer or hexene homopolymer (>1,300,000 g/mol) with narrow molecular weight distribution (Mw/Mn). The resulting inventive examples IE1-IE7 contain no titanium and contain residual zirconium (IE 1-5 also containing residual germanium).

[0118] Comparative examples using CGC, metallocene 1, or metallocene 2 resulted in significantly lower molecular weights when compared to IE1-IE7. Comparative example using ZN catalyst resulted in broad molecular weight distribution.

[0119] It is specifically intended that the present disclosure not be limited to the embodiments and illustrations contained herein, but include modified forms of those embodiments including portions of the embodiments and combinations of elements of different embodiments as come within the scope of the following claims.