EP2688923A2 - Polymères ramifiés à terminaison vinylique et procédés pour les produire - Google Patents

Polymères ramifiés à terminaison vinylique et procédés pour les produire

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Publication number
EP2688923A2
EP2688923A2 EP12762766.9A EP12762766A EP2688923A2 EP 2688923 A2 EP2688923 A2 EP 2688923A2 EP 12762766 A EP12762766 A EP 12762766A EP 2688923 A2 EP2688923 A2 EP 2688923A2
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EP
European Patent Office
Prior art keywords
borate
tetrakis
mol
chain ends
perfluoronaphthyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP12762766.9A
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German (de)
English (en)
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EP2688923A4 (fr
Inventor
Peijun Jiang
Patrick Brant
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ExxonMobil Chemical Patents Inc
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ExxonMobil Chemical Patents Inc
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Priority to EP20120762766 priority Critical patent/EP2688923A4/fr
Publication of EP2688923A2 publication Critical patent/EP2688923A2/fr
Publication of EP2688923A4 publication Critical patent/EP2688923A4/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+

Definitions

  • TITLE BRANCHED VINYL TERMINATED POLYMERS AND METHODS FOR PRODUCTION THEREOF INVENTORS: Peijun Jiang and Patrick Brant PRIORITY
  • This invention relates to olefin polymerization, particularly to produce vinyl terminated polymers.
  • Alpha-olefins especially those containing about 6 to about 20 carbon atoms, have been used as intermediates in the manufacture of detergents or other types of commercial products. Such alpha-olefins have also been used as comonomers, especially in linear low density polyethylene. Commercially produced alpha-olefins are typically made by oligomerizing ethylene. Longer chain alpha-olefins, such as vinyl-terminated polyethylenes are also known and can be useful as building blocks following functionalization or as macromonomers .
  • U.S. Patent No. 4,814,540 discloses bis(pentamethyl cyclopentadienyl) hafnium dichloride, bis(pentamethyl cyclopentadienyl) zirconium dichloride and bis(tetramethyl n-butyl cyclopentadienyl) hafnium dichloride with methylalumoxane in toluene or hexane with or without hydrogen to make allylic vinyl terminated propylene homo-oligomers having a low degree of polymerization of 2-10. These oligomers do not have high Mns and do not have at least 93% allylic vinyl unsaturation.
  • Weng et al. discloses materials with up to about 81% vinyl termination made using dimethylsilyl bis(2 -methyl, 4- phenyl-indenyl) zirconium dichloride and methylalumoxane in toluene at about 120°C.
  • the materials have a Mn of about 12,300 (measured with NMR) and a melting point of about 143°C.
  • Markel et al. discloses comb branch- block polyethylene made with Op ⁇ CXi and (C 5 Me4SiMe2NC 1 2H23) iCi2, activated with methyl alumoxane.
  • Moscardi, et al. (Organometallics, 20, 2001, pp. 1918) discloses the use of rac- dimethylsilylmethylenebis(3-t-butyl indenyl)zirconium dichloride with methylalumoxane in batch polymerizations of propylene to produce materials where ". . .allyl end group always prevails over any other end groups, at any [propene]." In these reactions, morphology control was limited and approximately 60% of the chain ends are allylic.
  • PHI ⁇ TiC ⁇ bis(phenoxyimine)titanium dichloride
  • MMAO modified methyl alumoxane
  • propylene was dissolved in toluene to create a 1.65 M toluene solution.
  • Catalyst productivity was very low (0.95 to 1.14 g/mmol Ti/hr).
  • JP 2005-336092 A2 discloses the manufacture of vinyl-terminated propylene polymers using materials such as H2SO4 treated montmorillonite, triethylaluminum, triisopropyl aluminum, where the liquid propylene is fed into a catalyst slurry in toluene. This process produces substantially isotactic macromonomers that do not have a significant amount of amorphous material.
  • U.S. Patent No. 6,897,261 discloses olefin graft copolymers obtained by copolymerizing an atactic branched macromonomer, wherein the macromonomer is derived from monomers selected from the group consisting of (1) propylene and (2) the combination of propylene and at least one selected from ethylene, alpha-olefins having from 4 to 20 carbon atoms, cyclic olefins and styrenes, and of which the propylene content falls between 0.1 mol% and 100 mol%, and which macromonomer satisfies the following (a) and (b): (a) its weight-average molecular weight (Mw) measured through gel permeation chromatography (GPC) falls between 400 and 200000; (b) its vinyl content is at least 70 mol% of all the unsaturated groups in the macromonomer, wherein the macromonomer satisfies each of the following (i), (ii), and (i
  • Rose, et al. discloses poly(ethylene-co- propylene) macromonomers not having significant amounts of iso-butyl chain ends. Those were made with bis(phenoxyimine) titanium dichloride ((PHT ⁇ TiC ⁇ ) activated with modified methylalumoxane (MMAO; Al/Ti molar ratio range 150 to 292) in semi-batch polymerizations (30 psi propylene added to toluene at 0°C for 30 min, followed by ethylene gas flow at 32 psi of over-pressure at about 0°C for polymerization times of 2.3 to 4 hours to produce E-P copolymer having an Mn of about 4,800 to 23,300. In four reported copolymerizations, allylic chain ends decreased with increasing ethylene incorporation roughly according to the equation:
  • % allylic chain ends (of total unsaturations) -0.95(mol% ethylene incorporated) + 100.
  • 65% allyl (compared to total unsaturation) was reported for E-P copolymer containing 29 mol% ethylene. This is the highest allyl population achieved.
  • 64 mol% incorporated ethylene only 42% of the unsaturations are allylic.
  • Productivity of these polymerizations ranged from 0.78 x 10 2 g/mmol Ti/hr to 4.62 x 10 2 g/mmol Ti/hr.
  • U.S. Patent No. 6,225,432 discloses branched polypropylene compositions which have improved melt strength and good processability.
  • the branched polypropylene compositions have a polydispersity of less than 4.0 and a melt point greater than 90°C.
  • the weight average branching index g of the polypropylene compositions is less than 0.95.
  • the invention relates to processes for polymerization, comprising:
  • M is selected from the group consisting of zirconium or hafnium
  • each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof, (two X's may form a part of a fused ring or a ring system);
  • each R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 is, independently, hydrogen or a substituted or unsubstituted hydrocarbyl group, a heteroatom or heteroatom containing group;
  • any two adjacent R groups may form a fused ring or multicenter fused ring system where the rings may be aromatic, partially saturated or saturated;
  • any of adjacent R 4 , R 5 , and R 6 groups may form a fused ring or multicenter fused ring system where the rings may be aromatic, partially saturated or saturated;
  • T is a bridging group represented by the formula R-2 a J, where J is one or more of C, Si, Ge, N, or P, and each R a is, independently, hydrogen, halogen, Q to C20 hydrocarbyl or a Q to C20 substituted hydrocarbyl,
  • R 3 is a substituted or unsubstituted phenyl group, if any of R 1 , R 2 , R 4 , R 5 or R 6 are not hydrogen;
  • This invention also relates to a branched polyolefin having an Mn ( ⁇ H NMR) of 7,500 to 60,000 g/mol comprising one or more alpha olefin derived units comprising ethylene and/or propylene, and having:
  • This invention also relates to branched polyolefins having an Mn (GPC) greater than 60,000 g/mol comprising one or more alpha olefins comprising ethylene and/or propylene, and having: (i) 50% or greater allyl chain ends, relative to total unsaturated chain ends; (ii) a g'vis of 0.90 or less; and optionally; and (iii) a bromine number which, upon complete hydrogenation, decreases by at least 50%.
  • Mn Mn
  • the invention further relates to branched polyolefins having an Mn ( ⁇ H NMR) of less than 7,500 g/mol comprising one or more alpha olefin derived units comprising ethylene and/or propylene, and having:
  • Figure 1 is a plot of the relationship between g'vis and log Mw for allyl terminated branched polypropylene polymers made with Metallocene A/Activator III (Examples, Table 3, Runs 59-65).
  • the inventors have surprisingly discovered new processes to make branched polyolefins having high amounts of allyl terminations. These new processes can be run under commercial conditions and are capable of producing the branched polyolefins at commercial rates. Furthermore, these processes are typically run using non-coordinating anion activators, preferably bulky activators, as defined below.
  • Branched as used herein, means a polyolefin having a g'vis of 0.90 or less, or if the polyolefin has a Mn ( ⁇ H MNR) of less than 7,500 g/mol, the branched polyolefin has a ratio of saturated chain ends to percentage of allyl chain ends of 1.2 to 2.0.
  • branched polyolefins having high amounts of allyl chain ends may find utility as macromonomers for the synthesis of branched poly(macromonomers), block copolymers, and as additives, for example, as additives to, or blending agents in, lubricants, waxes, and adhesives.
  • additives for example, as additives to, or blending agents in, lubricants, waxes, and adhesives.
  • the branched nature of these polyolefins may improve the desired mechanical properties by allowing optimal thermoforming and molding at lower temperatures, thereby reducing energy consumption of the film forming process, as compared to linear polyolefin analogues.
  • the high amounts of allyl chain ends of these branched polyolefins provides a facile path to functionalization.
  • the functionalized branched polyolefins may be also useful as additives or blending agents.
  • Catalyst productivity is a measure of how many kilograms of polymer (P) are produced using a polymerization catalyst comprising W moles of catalyst (W); and may be expressed in units of kilograms of polymer per mole of catalyst.
  • Conversion is the amount of monomer that is converted to polymer product, and is reported as mol% and is calculated based on the polymer yield and the amount of monomer fed into the reactor.
  • Catalyst activity is a measure of how active the catalyst is and is reported as the mass of product polymer (P) produced per kg of catalyst (cat) used (kgP/kgcat).
  • an "olefin,” alternatively referred to as “alkene,” is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond.
  • alkene is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond.
  • a polymer or copolymer is referred to as comprising an olefin, including, but not limited to ethylene, propylene, and butene
  • the olefin present in such polymer or copolymer is the polymerized form of the olefin.
  • a copolymer 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.
  • the term "polymer,” as used herein, includes oligomers (up to 100 mer units), and larger polymers (greater than 100 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.
  • a “terpolymer” is a polymer having three 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. Accordingly, the definition of copolymer, as used herein, includes terpolymers and the like.
  • Mn is number average molecular weight (measured by NMR, unless stated otherwise)
  • Mw is weight average molecular weight (measured by Gel Permeation Chromatography, GPC)
  • Mz is z average molecular weight (measured by GPC)
  • wt% is weight percent
  • mol% is mole percent
  • vol% is volume percent
  • mol mole.
  • Molecular weight distribution (MWD) is defined to be Mw divided by Mn (measured by GPC), Mw/Mn. Unless otherwise noted, all molecular weights (e.g., Mw, Mn, Mz) have units of g/mol. Also, room temperature is 23 °C unless otherwise noted.
  • Bromine number is determined by ASTM D 1159.
  • This invention relates to a process for polymerization, comprising:
  • M is selected from the group consisting of zirconium or hafnium (preferably hafnium);
  • each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof, (two X's may form a part of a fused ring or a ring system) (preferably X is a halide or a hydrocarbyl radical having from 1 to 20 carbon atoms, preferably X is chloride or methyl);
  • each R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 is, independently, hydrogen or a substituted or unsubstituted hydrocarbyl group, a heteroatom or heteroatom containing group;
  • any two adjacent R groups may form a fused ring or multicenter fused ring system where the rings may be aromatic, partially saturated or saturated;
  • any of adjacent R 4 , R 5 , and R 6 groups may form a fused ring or multicenter fused ring system where the rings may be aromatic, partially saturated or saturated;
  • T is a bridging group represented by the formula R2 a J, where J is one or more of C, Si, Ge, N, or P (preferably J is Si), and each R a is, independently, hydrogen, halogen, Q to C20 hydrocarbyl or a Q to C20 substituted hydrocarbyl (preferably R a is methyl, ethyl, chloride), provided that at least one R 3 , preferably both, are a substituted or unsubstituted phenyl group, if any of R 1 , R 2 , R 4 , R 5 or R 6 are not hydrogen;
  • the productivity is 4500 g/mmol or more, preferably 5000 g/mmol or more, preferably 10,000 g/mmol or more, preferably 50,000 g/mmol or more. In other embodiments, the productivity is at least 80,000 g/mmol, preferably at least 150,000 g/mmol, preferably at least 200,000 g/mmol, preferably at least 250,000 g/mmol, preferably at least 300,000 g/mmol.
  • the activity of the catalyst is at least 10,000 kg polymer per kg catalyst, preferably 50,000 or more kg polymer per kg catalyst, preferably 100,000 or more kg polymer per kg catalyst, preferably 150,000 or more kg polymer per kg catalyst.
  • the conversion of olefin monomer is at least 50 mol%, based upon the weight of the monomer entering the reaction zone, preferably 60 mol% or more, preferably 70 mol% or more, preferably 80 mol% or more.
  • Typical temperatures and/or pressures include a temperature greater than 35°C (preferably in the range of from about 35 to 150°C, from 40 to 140°C, from 60 to 140°C, or from 80 to 130°C) and a pressure in the range of from about 0.35 to 10 MPa (preferably from 0.45 to 6 MPa or from 0.5 to 4 MPa).
  • the inventive processes described herein have a residence time suitable for commercial production of these branched vinyl terminated polymers.
  • the residence time of the polymerization process is up to 300 minutes, preferably in the range of from about 1 to 300 minutes, preferably from 5 to 250 minutes, preferably from about 10 to 120 minutes, or preferably from about 10 to 60 minutes.
  • Suitable diluents/solvents for polymerization include non-coordinating, inert liquids.
  • examples include straight and branched-chain hydrocarbons such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as can be found commercially (IsoparTM); and perhalogenated hydrocarbons such as perfluorinated C4 0 alkanes.
  • straight and branched-chain hydrocarbons such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecan
  • Suitable solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, 1 -butene, 1-hexene, 1-pentene, 3 -methyl- 1- pentene, 4-methyl- 1-pentene, 1-octene, 1-decene, and mixtures thereof.
  • aliphatic hydrocarbons are used as the solvent, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof.
  • the solvent is not aromatic, preferably aromatics are present in the solvent at less than 1 wt%, preferably at 0.5 wt%, preferably at 0 wt% based upon the weight of the solvents.
  • the feed concentration for the polymerization is 60 vol% solvent or less, preferably 40 vol% or less, or preferably 20 vol% or less, preferably 0 vol% based on the total volume of the feedstream.
  • the polymerization is run in a bulk process.
  • the butene source may be a mixed butene stream comprising various isomers of butene.
  • the 1 -butene monomers are expected to be preferentially consumed by the polymerization process.
  • Use of such mixed butene streams will provide an economic benefit, as these mixed streams are often waste streams from refining processes, for example C 4 raffinate streams, and can therefore be substantially less expensive than pure 1 -butene.
  • Processes of this invention can be carried out in any manner known in the art. Any suspension, homogeneous bulk, solution, slurry, or gas phase polymerization process known in the art can be used. Such processes can be run in a batch, semi-batch, or continuous mode. Homogeneous polymerization processes and slurry are preferred. (A homogeneous polymerization process is defined to be a process where at least 90 wt% of the product is soluble in the reaction media.) A bulk homogeneous process is particularly preferred.
  • a bulk process is defined to be a process where monomer concentration in all feeds to the reactor is 70 vol% or more.
  • no solvent or diluent is present or added in the reaction medium, (except for the small amounts used as the carrier for the catalyst system or other additives, or amounts typically found with the monomer; e.g., propane in propylene).
  • the process is a single stage polymerization process.
  • the process is a slurry process.
  • slurry polymerization process means a polymerization process where a supported catalyst is employed and monomers are polymerized on the supported catalyst particles.
  • At least 95 wt% of polymer products derived from the supported catalyst are in granular form as solid particles (not dissolved in the diluent).
  • continuous mode is meant that there is continuous addition to, and withdrawal of reactants and products from, the reactor system. Continuous processes can be operated in steady state; i.e., the composition of effluent remains fixed with time if the flow rate, temperature/pressure and feed composition remain invariant. For example, a continuous process to produce a polymer would be one where the reactants are continuously introduced into one or more reactors and polymer product is continuously withdrawn.
  • hydrogen is present in the polymerization reactor at a partial pressure of 0.001 to 50 psig (0.007 to 345 kPa), preferably from 0.01 to 25 psig (0.07 to 172 kPa), more preferably 0.1 to 10 psig (0.7 to 70 kPa). It has been found that in the present systems, hydrogen can be used to provide increased activity without significantly impairing the catalyst's ability to produce allylic chain ends.
  • the catalyst activity (calculated as g/mmol catalyst/hr) is at least 20% higher than the same reaction without hydrogen present, preferably at least 50% higher, preferably at least 100% higher.
  • reaction vessels include reactors (including continuous stirred tank reactors, batch reactors, reactive extruder, pipe or pump.
  • a "reaction zone” also referred to as a "polymerization zone” is defined as an area where activated catalysts and monomers are contacted and a polymerization reaction takes place.
  • each reactor is considered as a separate polymerization zone.
  • each polymerization stage is considered as a separate polymerization zone.
  • the polymerization described herein occurs within a single reaction zone. Alternately the polymerization described herein may occur in multiple reaction zones.
  • hydrogen is present in the polymerization reactor at a partial pressure of 0.001 to 50 psig (0.007 to 345 kPa), preferably from 0.01 to 25 psig (0.07 to 172 kPa), more preferably 0.1 to 10 psig (0.7 to 70 kPa). It has been found that in the present systems, hydrogen can be used to provide increased activity without significantly impairing the catalyst's ability to produce allylic chain ends.
  • the catalyst activity (calculated as g/mmol catalyst/hr) is at least 20% higher than the same reaction without hydrogen present, preferably at least 50% higher, preferably at least 100% higher.
  • alumoxane is present at zero mol%, alternately the alumoxane is present at a molar ratio of aluminum to transition metal less than 500: 1, preferably less than 300: 1, preferably less than 100: 1, preferably less than 1 : 1.
  • an alumoxane is used to produce the vinyl terminated polymers, then the alumoxane has been treated to remove free alkyl aluminum compounds, particularly trimethyl aluminum.
  • the activator used herein to produce the vinyl terminated polymer is a bulky activator as defined herein and is discrete.
  • scavenger such as tri alkyl aluminum
  • the scavenger is present at zero mol%, alternately the scavenger is present at a molar ratio of scavenger metal to transition metal of less than 100: 1, preferably less than 50: 1, preferably less than 15: 1, preferably less than 10: 1.
  • the polymerization 1) is conducted at temperatures of 0 to 300°C (preferably 25 to 150°C, preferably 40 to 120°C, preferably 45 to 80°C); 2) is conducted at a pressure of atmospheric pressure to 10 MPa (preferably 0.35 to 10 MPa, preferably from 0.45 to 6 MPa, preferably from 0.5 to 4 MPa); 3) is conducted in an aliphatic hydrocarbon solvent (such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; preferably where aromatics are present in the solvent at less than 1 wt%, preferably at 0.5 wt%, preferably at 0
  • the catalyst system used in the polymerization comprises no more than one catalyst compound.
  • a "reaction zone” also referred to as a "polymerization zone” is a vessel where polymerization takes place, for example a batch reactor. When multiple reactors are used in either series or parallel configuration, each reactor is considered as a separate polymerization zone. For a multi-stage polymerization in both a batch reactor and a continuous reactor, each polymerization stage is considered as a separate polymerization zone. In a preferred embodiment, the polymerization occurs in one reaction zone. Room temperature is 23°C unless otherwise noted.
  • the invention relates to processes for making vinyl terminated branched polyolefins at commercial rates and under commercial conditions, wherein the process comprises contacting the monomers in the presence of a catalyst system comprising a metallocene catalyst compound and an activator capable of producing branched polyolefins having 50% or more allyl chain ends.
  • a catalyst system comprising a metallocene catalyst compound and an activator capable of producing branched polyolefins having 50% or more allyl chain ends.
  • the catalyst system is a mixed catalyst system comprising one or more non-metallocene catalyst compounds, one or more metallocene catalyst compounds, or a combination thereof, preferably the mixed catalyst system comprises two or more metallocene catalyst compounds.
  • the catalyst system is a single catalyst system.
  • one, two, or more activators may be used in the catalyst system.
  • the catalyst may be described as a catalyst precursor, a pre-catalyst compound, a catalyst compound, or a transition metal compound, and these terms are used interchangeably.
  • a polymerization catalyst system is a catalyst system that can polymerize monomers to polymer.
  • a “catalyst system” is a combination of at least one catalyst compound, at least one activator, an optional co-activator, and an optional support material.
  • An "anionic ligand” is a negatively charged ligand which donates one or more pairs of electrons to a metal ion.
  • a “neutral donor ligand” is a neutrally charged ligand which donates one or more pairs of electrons to a metal ion.
  • catalyst systems are described as comprising neutral stable forms of the components, it is well understood by one of ordinary skill in the art, that the ionic form of the component is the form that reacts with the monomers to produce polymers.
  • a metallocene catalyst is defined as an organometallic compound with at least one ⁇ -bound cyclopentadienyl moiety (or substituted cyclopentadienyl moiety) and more frequently two ⁇ -bound cyclopentadienyl-moieties or substituted moieties. This includes other ⁇ -bound moieties such as indenyls or fluorenyls or derivatives thereof.
  • a “hydrocarbyl” is a radical made of hydrogen and carbon.
  • substituted means that a hydrogen group has been replaced with a hydrocarbyl group, a heteroatom, or a heteroatom containing group.
  • methyl cyclopentadiene (Cp) is a Cp group substituted with a methyl group
  • ethyl alcohol is an ethyl group substituted with an -OH group
  • substituted hydrocarbyl is a radical made of carbon and hydrogen where at least one hydrogen is replaced by a heteroatom.
  • alkoxides include those where the alkyl group is a to C 4 Q hydrocarbyl.
  • the alkyl group may be straight chain, branched, or cyclic.
  • the alkyl group may be saturated or unsaturated.
  • the alkyl group may comprise at least one aromatic group.
  • the metallocene catalyst compound of the catalyst system is represented by the formula:
  • M is selected from the group consisting of zirconium or hafnium (preferably hafnium); each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof, (two X's may form a part of a fused ring or a ring system) (preferably X is a halide or a hydrocarbyl radical having from 1 to 20 carbon atoms, preferably X is chloride or methyl);
  • each R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 is, independently, hydrogen or a substituted or unsubstituted hydrocarbyl group, a heteroatom or heteroatom containing group;
  • any two adjacent R groups may form a fused ring or multicenter fused ring system where the rings may be aromatic, partially saturated or saturated;
  • any of adjacent R 4 , R 5 , and R 6 groups may form a fused ring or multicenter fused ring system where the rings may be aromatic, partially saturated or saturated;
  • T is a bridging group represented by the formula R2 a J, where J is one or more of C, Si, Ge, N, or P (preferably J is Si), and each R a is, independently, hydrogen, halogen, Q to C20 hydrocarbyl or a Q to C20 substituted hydrocarbyl, (preferably R a is methyl, ethyl, chloride), provided that at least one R 3 , preferably both, are a substituted or unsubstituted phenyl group, if any of R 1 , R 2 , R 4 , R 5 or R 6 are not hydrogen;
  • R a substituent groups include a Q to C20 hydrocarbyls, such as methyl, ethyl, propyl (including isopropyl, sec -propyl), butyl (including t-butyl and sec -butyl), neopentyl, cyclopentyl, hexyl, octyl, nonyl, decyl, phenyl, substituted phenyl, benzyl (including substituted benzyl), cyclohexyl, cyclododecyl, norbornyl, and all isomers thereof.
  • Q to C20 hydrocarbyls such as methyl, ethyl, propyl (including isopropyl, sec -propyl), butyl (including t-butyl and sec -butyl), neopentyl, cyclopentyl, hexyl, octyl, nonyl, decyl
  • the bridging group R 2 a T comprises carbon or silica, such as dialkylsilyl, preferably the bridging group is selected from CH 2 , CH 2 CH 2 , C(CH 3 ) 2 , SiMe 2 , SiPh 2 , SiMePh, and (Ph) 2 C.
  • Catalyst compounds that are particularly useful in this invention include one or more of:
  • the "dimethyl" after the transition metal in the list of catalyst compounds above is replaced with a dihalide (such as dichloride or difluoride) or a bisphenoxide.
  • hafnium in the list of catalyst compounds above is replaced with zirconium.
  • zirconium in the list of catalyst compounds above is replaced with hafnium.
  • activator is used herein interchangeably and are defined to be any compound which can activate any one of the catalyst compounds described above by converting the neutral catalyst compound to a catalytically active catalyst compound cation.
  • Non-limiting activators include ionizing activators, which may be neutral or ionic, and conventional-type cocatalysts.
  • Preferred activators typically include ionizing anion precursor compounds that abstract one reactive, ⁇ -bound, metal ligand making the metal complex cationic and providing a charge-balancing noncoordinating or weakly coordinating anion.
  • alumoxane is present at zero mol%, alternately the alumoxane is present at a molar ratio of aluminum to transition metal less than 500: 1, preferably less than 300: 1, preferably less than 100: 1, preferably less than 1 : 1.
  • the alumoxane has been treated to remove free alkyl aluminum compounds, particularly trimethyl aluminum.
  • the activator used herein to produce the branched polyolefins is bulky as defined herein and is discrete.
  • an ionizing or stoichiometric activator 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. Patent No. 5,942,459) or combination thereof.
  • neutral or ionic activators alone or in combination with alumoxane or modified alumoxane activators. Much preferred activators are the ionic ones, not the neutral boranes.
  • 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.
  • 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. Most preferably, the neutral stoichiometric activator is tris perfluorophenyl boron or tris perfluoronaphthyl boron.
  • Ionic stoichiometric activator compounds may contain an active proton, or some other cation associated with, but not coordinated to, or only loosely coordinated to, the remaining ion of the ionizing compound. Such compounds and the like are described in
  • EP 0 570 982 A EP 0 520 732 A; EP 0 495 375 A; EP 0 500 944 B l;
  • Ionic catalysts can be prepared by reacting a transition metal compound with some neutral Lewis acids, such as B(C6F 6 ) 3 , which upon reaction with the hydro lyzable ligand (X) of the transition metal compound forms an anion, such as ([B(C6F 5 ) 3 (X)]-), which stabilizes the cationic transition metal species generated by the reaction.
  • the catalysts can be, and preferably are, prepared with activator components which are ionic compounds or compositions.
  • Compounds useful as an activator component in the preparation of the ionic catalyst systems used 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.
  • a cation which is preferably a Bronsted acid capable of donating a proton
  • a compatible non-coordinating anion which anion is relatively large (bulky)
  • the active catalyst species the Group 4 cation
  • the stoichiometric activators include a cation and an anion component, and may be represented by the following formula:
  • L is a neutral Lewis base
  • H is hydrogen
  • (L-H) + is a Bronsted acid
  • a d_ is a non- coordinating anion having the charge d-
  • d is 1, 2, or 3.
  • the cation component, (L-H) d + 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.
  • 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.
  • the activating cation (L-H) ⁇ "1" may be 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, ⁇ , ⁇ -dimethylaniline, methyldiphenylamine, pyridine, p-bromo ⁇ , ⁇ -dimethylaniline, p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine, triphenylphosphine, and diphenylphosphine, oxoniums from ethers, such as dimethyl ether diethyl ether, tetrahydrofuran,
  • 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.
  • suitable A d_ also include diboron compounds as disclosed in U.S. Patent No. 5,447,895, which is fully incorporated herein by reference.
  • trimethylammonium tetraphenylborate triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, tri(t- butyl)ammonium tetraphenylborate, ⁇ , ⁇ -dimethylanilinium tetraphenylborate, N,N- diethylanilinium tetraphenylborate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetraphenylborate, tropillium tetraphenylborate, triphenylcarbenium tetraphenylborate, triphenylphosphonium tetraphenylborate triethylsilylium tetraphenylborate, benzene(diazonium)tetraphenylborate, trimethylammonium t
  • the ionic stoichiometric activator (L-H) d + (A d_ ) is, N,N- dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, ⁇ , ⁇ -dimethylanilinium tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, or triphenylcarbenium tetrakis(perfluorophenyl)borate.
  • an activation method using ionizing ionic compounds not containing an active proton but capable of producing a bulky ligand metallocene catalyst cation and their non-coordinating anion are also contemplated, and are described in EP 0 426 637 A, EP 0 573 403 A, and U.S. Patent No. 5,387,568, which are all herein incorporated by reference.
  • non-coordinating anion means an anion which either does not coordinate to said cation or which is only weakly coordinated to said 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 four coordinate metallocene 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 metallocene cation in the sense of balancing its ionic charge at +1, yet retain sufficient lability to permit displacement by an ethylenically or acetylenically unsaturated monomer during polymerization.
  • scavengers are used such as tri-isobutyl aluminum or tri-octyl aluminum.
  • the activator is a non-coordinating anion activator.
  • Inventive processes also can employ cocatalyst compounds or activator compounds that are initially neutral Lewis acids but form a cationic metal complex and a noncoordinating anion, or a zwitterionic complex upon reaction with the invention compounds.
  • tris(pentafluorophenyl) boron or aluminum act to abstract a hydrocarbyl or hydride ligand to yield an invention cationic metal complex and stabilizing noncoordinating anion, see EP 0 427 697 A and EP 0 520 732 A for illustrations of analogous Group-4 metallocene compounds.
  • EP 0 495 375 A for formation of zwitterionic complexes using analogous Group 4 compounds.
  • Another suitable ion forming, activating cocatalyst comprises a salt of a cationic oxidizing agent and a noncoordinating, compatible anion represented by the formula:
  • OX e+ is a cationic oxidizing agent having a charge of e+; e is 1, 2, or 3; and A d" is a non-coordinating anion having the charge d-; and d is 1 2, or 3.
  • cationic oxidizing agents include: ferrocenium, hydrocarbyl-substituted ferrocenium, Ag + or Pb +2 .
  • Preferred embodiments of A d" are those anions previously defined with respect to the Bronsted acid containing activators, especially tetrakis(pentafluorophenyl)borate.
  • the typical NCA (or non-alumoxane activator) activator-to-catalyst ratio is a 1 : 1 molar ratio.
  • Alternate preferred ranges include from 0.1 : 1 to 100: 1, alternately from 0.5: 1 to 200: 1, alternately from 1 : 1 to 500: 1, alternately from 1 : 1 to 1000: 1.
  • a particularly useful range is from 0.5: 1 to 10: 1, preferably 1 : 1 to 5: 1.
  • Bulky activators can advantageously produce higher Mw, higher Tm, and/or a greater amount of allyl chain ends than the same catalyst with a non-bulky activator, under the same polymerization conditions.
  • Bulky activator refers to anionic activators represented by the formula:
  • each R 1 is, independently, a halide, preferably a fluoride
  • each R 2 is, independently, a halide, a to C20 substituted aromatic hydrocarbyl group or a siloxy group of the formula -0-Si-R a , where R a is a Q to C20 hydrocarbyl or hydrocarbylsilyl group (preferably R2 is a fluoride or a perfluorinated phenyl group);
  • each R 3 is a halide, to C20 substituted aromatic hydrocarbyl group or a siloxy group of the formula -0-Si-R a , where R a is a Ci to C20 hydrocarbyl or hydrocarbylsilyl group (preferably R3 is a fluoride or a perfluorinated aromatic hydrocarbyl group); wherein R2 and R3 can form one or more saturated or unsaturated, substituted or unsubstituted rings (preferably R2 and R3 form a perfluorinated phenyl ring);
  • L is an neutral Lewis base
  • d is 1, 2, or 3;
  • the anion has a molecular weight of greater than 1020 g/mol
  • 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.
  • V s is 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 V s is decreased by 7.5% per fused ring.
  • Exemplary bulky activators useful in catalyst systems herein include: trimethylammonium tetrakis(perfluoronaphthyl)borate, triethylammonium tetrakis(perfluoronaphthyl)borate, tripropylammonium tetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammonium tetrakis(perfluoronaphthyl)borate, tri(t-butyl)ammonium tetrakis(perfluoronaphthyl)borate, ⁇ , ⁇ -dimethylanilinium tetrakis(perfluoronaphthyl)borate, ⁇ , ⁇ -diethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethyl-(2,4,6- trimethylanilinium) tetrakis
  • catalyst compounds can be combined with one or more activators or activation methods described above.
  • Aluminum alkyl or organoaluminum compounds which may be utilized as co- activators (or scavengers) include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum.
  • the catalyst system may comprise an inert support material.
  • the supported material is a porous support material, for example, talc, and inorganic oxides.
  • Other support materials include zeolites, clays, organoclays, or any other organic or inorganic support material, and the like, or mixtures thereof.
  • the support material is an inorganic oxide in a finely divided form. Suitable inorganic oxide materials for use in metallocene catalyst systems herein include Groups 2, 4, 13, and 14 metal oxides such as silica, alumina, and mixtures thereof.
  • inorganic oxides that may be employed either alone or in combination with the silica, or alumina are magnesia, titania, zirconia, and the like.
  • suitable support materials can be employed, for example, finely divided functionalized polyolefins such as finely divided polyethylene.
  • Particularly useful supports include magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolites, talc, clays, and the like.
  • combinations of these support materials may be used, for example, silica-chromium, silica-alumina, silica-titania and the like.
  • Preferred support materials include AI2O3, ⁇ 3 ⁇ 4, S1O2, and combinations thereof, more preferably S1O2, AI2O3, or S1O2/AI2O3.
  • the support material most preferably an inorganic oxide, has a surface area in the range of from about 10 to about 700 m 2 /g, pore volume in the range of from about 0.1 to about 4.0 cc/g and average particle size in the range of from about 5 to about 500 ⁇ . More preferably, the surface area of the support material is in the range of from about 50 to about 500 m 2 /g, pore volume of from about 0.5 to about 3.5 cc/g and average particle size of from about 10 to about 200 ⁇ .
  • the surface area of the support material is in the range of from about 100 to about 400 m 2 /g, pore volume from about 0.8 to about 3.0 cc/g and average particle size is from about 5 to about 100 ⁇ .
  • the average pore size of the support material useful in the invention is in the range of from 10 to 1000 A, preferably 50 to about 500 A, and most preferably 75 to about 350 A.
  • the support material should be dry, that is, free of absorbed water. Drying of the support material can be effected by heating or calcining at about 100°C to about 1000°C, preferably at least about 600°C. When the support material is silica, it is heated to at least 200°C, preferably about 200°C to about 850°C, and most preferably at about 600°C; and for a time of about 1 minute to about 100 hours, from about 12 hours to about 72 hours, or from about 24 hours to about 60 hours.
  • the calcined support material must have at least some reactive hydroxyl (OH) groups to produce the catalyst system of this invention.
  • the calcined support material is then contacted with at least one polymerization catalyst comprising at least one metallocene compound and an activator.
  • the support material having reactive surface groups, typically hydroxyl groups, is slurried in a non-polar solvent and the resulting slurry is contacted with a solution of a metallocene compound and an activator.
  • the slurry of the support material in the solvent is prepared by introducing the support material into the solvent, and heating the mixture to about 0 to about 70°C, preferably to about 25 to about 60°C, preferably at room temperature. Contact times typically range from about 0.5 hours to about 24 hours, from about 0.5 hours to about 8 hours, or from about 0.5 hours to about 4 hours.
  • Suitable non-polar solvents are materials in which all of the reactants used herein, i.e., the activator, and the metallocene compound, are at least partially soluble and which are liquid at reaction temperatures.
  • Preferred non-polar solvents are alkanes, such as isopentane, hexane, n-heptane, octane, nonane, and decane, although a variety of other materials including cycloalkanes, such as cyclohexane, aromatics, such as benzene, toluene and ethylbenzene, may also be employed.
  • the support material is contacted with a solution of a metallocene compound and an activator, such that the reactive groups on the support material are titrated, to form a supported polymerization catalyst.
  • the period of time for contact between the metallocene compound, the activator, and the support material is as long as is necessary to titrate the reactive groups on the support material.
  • titrate is meant to react with available reactive groups on the surface of the support material, thereby reducing the surface hydroxyl groups by at least 80%, at least 90%, at least 95%, or at least 98%.
  • the surface reactive group concentration may be determined based on the calcining temperature and the type of support material used.
  • the support material calcining temperature affects the number of surface reactive groups on the support material available to react with the metallocene compound and an activator: the higher the drying temperature, the lower the number of sites.
  • the support material is silica which, prior to the use thereof in the first catalyst system synthesis step, is dehydrated by fluidizing it with nitrogen and heating at about 600°C for about 16 hours, a surface hydroxyl group concentration of about 0.7 millimoles per gram (mmols/gm) is typically achieved.
  • mmols/gm millimoles per gram
  • the exact molar ratio of the activator to the surface reactive groups on the carrier will vary. Preferably, this is determined on a case-by-case basis to assure that only so much of the activator is added to the solution as will be deposited onto the support material without leaving excess of the activator in the solution.
  • the amount of the activator which will be deposited onto the support material without leaving excess in the solution can be determined in any conventional manner, e.g., by adding the activator to the slurry of the carrier in the solvent, while stirring the slurry, until the activator is detected as a solution in the solvent by any technique known in the art, such as by !fi NMR.
  • the amount of the activator added to the slurry is such that the molar ratio of B to the hydroxyl groups (OH) on the silica is about 0.5: 1 to about 4: 1, preferably about 0.8: 1 to about 3: 1, more preferably about 0.9: 1 to about 2: 1 and most preferably about 1 : 1.
  • the amount of boron on the silica may be determined by using ICPES (Inductively Coupled Plasma Emission Spectrometry), which is described in J. W. Olesik, "Inductively Coupled Plasma- Optical Emission Spectroscopy," in the Encyclopedia of Materials Characterization, C. R. Brundle, C. A. Evans, Jr. and S. Wilson, Eds., Butterworth-Heinemann, Boston, Mass., 1992, pp. 633-644.
  • ICPES Inductively Coupled Plasma Emission Spectrometry
  • Embodiments herein relate to branched polyolefins having allyl chain ends of 50% or more.
  • the inventors have surprisingly found that the processes disclosed herein give rise to an increased population of long chain branched products, possibly through vinyl macromonomer re-incorporation. Without wishing to be bound by theory, the inventors opine that the branching is likely of the "T" variety, and these branched polyolefins retain high amounts of allyl chain ends.
  • branched polyolefins having 50% or more allyl chain ends produced by the processes disclosed herein is:
  • (b) has at least 50% allyl chain ends, relative to total unsaturated chain ends (preferably 60% or more, preferably 70% or more, preferably 75% or more, preferably 80% or more, preferably 90% or more, preferably 95% or more) and having at least one of:
  • an allyl chain end to vinyl ene chain end ratio of greater than 1 : 1 (preferably greater than 2: 1, greater than 5: 1, or greater than 10: 1).
  • the branched polyolefins have an Mn (measured by l R NMR) of 7,500 to 60,000 g/mol, the branched polyolefin has:
  • a branching index (g'vis) of less than 0.90 preferably less than 0.85, less than 0.80, or less than 0.75
  • g'vis shall be used (if g'vis cannot be determined, then the ratio of percentage of saturated chain ends to percentage of allyl chain ends shall be used; if the ratio of percentage of saturated chain ends to percentage of allyl chain ends cannot be determined, then the ratio of Mn(GPC)/Mn( 1 H NMR) shall be used).
  • the branched polyolefins have an Mn (measured by GPC) of greater than 60,000 g/mol
  • the branched polyolefin has a g'vis of less than 0.90 (preferably 0.85 or less, preferably 0.80 or less) and, optionally, a bromine number which, upon complete hydrogenation, decreases by at least 50% (preferably by at least 75%).
  • the branched polyolefins have an Mn (measured by !fi NMR) of less than 7,500 g/mol (preferably from 100 to 7,500 g/mol), comprise one or more alpha olefins (preferably propylene and/or ethylene, preferably propylene) and, optionally, a C 4 to C 4 o alpha olefin (preferably a C 4 to C20 alpha olefin, preferably a C 4 to alpha olefin, preferably butene, pentene, hexene, heptene, octene, nonene, decene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, and isomers thereof), and have:
  • the branched polyolefins having an Mn (measured by !H NMR) of less than 7,500 g/mol (preferably from 100 to 7,500 g/mol) has a g'vis of 0.90 or less (preferably 0.85 or less, preferably 0.80 or less).
  • the branched polyolefins produced herein have an Mn (measured by l R NMR) of 7,500 to 60,000 g/mol, comprise one or more alpha olefins (preferably propylene and/or ethylene, preferably propylene) and, optionally, a C 4 to C 4 Q alpha olefin (preferably a C 4 to C20 alpha olefin, preferably a C 4 to alpha olefin, preferably butene, pentene, hexene, heptene, octene, nonene, decene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, and isomers thereof), and have:
  • a g'vis of 0.90 or less (preferably 0.85 or less, preferably 0.80 or less); and/or a ratio of percentage of saturated chain ends (preferably isobutyl chain ends) to percentage of allyl chain ends of 1.2 to 2.0 (preferably 1.6 to 1.8), wherein the percentage of saturated chain ends is determined using 13 C NMR as described in WO 2009/155471 at paragraph [0095] and [0096] except that the spectra are referenced to the chemical shift of the solvent, tetrachloroethane-d 2 , and/or a ratio of MntGPCyMn ⁇ H NMR) of 0.95 or less (preferably 0.90 or less, preferably 0.85 or less, preferably 0.80 or less);
  • a peak melting point (Tm) of greater than 60°C preferably greater than 100°C, preferably from 60 to 180°C, preferably from 80 to 175°C;
  • Hf heat of fusion
  • an allyl chain end to vinylene chain end ratio of greater than 1 : 1 (preferably greater than 2: 1, greater than 5: 1, or greater than 10: 1).
  • the branched polyolefins produced herein have an Mn (measured by GPC) of greater than 60,000 g/mol, comprise one or more alpha olefins (preferably propylene and/or ethylene, preferably propylene) and optionally, a C 4 to C 4 Q alpha olefin (preferably a C 4 to C20 alpha olefin, preferably a C 4 to alpha olefin, preferably butene, pentene, hexene, heptene, octene, nonene, decene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, and isomers thereof) and have:
  • Tm optionally, a Tm of greater than 60°C (preferably greater than 100°C, preferably from 60 to 180°C, preferably from 80 to 175°C);
  • (v) optionally, an Hf of greater than 7 J/g (preferably greater than 15 J/g, greater than 30 J/g, greater than 50 J/g, greater than 60 J/g, or greater than 80 J/g).
  • the branched polyolefins produced herein have an Mn (measured by l R NMR) of less than 7,500 g/mol (preferably from 100 to 7,500 g/mol), comprise one or more alpha olefins (preferably propylene and/or ethylene, preferably propylene) and, optionally, a C 4 to C 4 Q alpha olefin (preferably a C 4 to C20 alpha olefin, preferably a C 4 to alpha olefin, preferably butene, pentene, hexene, heptene, octene, nonene, decene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, and isomers thereof) and have:
  • Tm optionally, a Tm of greater than 60°C (preferably greater than 100°C, preferably from 60 to 180°C, preferably from 80 to 175°C);
  • an Hf of greater than 7 J/g preferably greater than 15 J/g, greater than 30 J/g, greater than 50 J/g, greater than 60 J/g, or greater than 80 J/g;
  • an allyl chain end to vinylene chain end ratio of greater than 1 : 1 (preferably greater than 2: 1, greater than 5: 1, or greater than 10: 1).
  • the branched polyolefins have a branching index, g'vis (as determined by GPC), of 0.90 or less (preferably 0.85 or less, preferably 0.80 or less), relative to a linear polymer of the same composition and microstructure.
  • g'vis as determined by GPC
  • the preferred branched polyolefins described herein have an Mn (measured by NMR) of 7,500 to 60,000 g/mol or alternately greater than 60,000 g/mol or alternately from 100 g/mol to less than 7,500 g/mol.
  • Mn measured by NMR
  • a desirable molecular weight range can be any combination of any upper molecular weight limit with any lower molecular weight limit described above.
  • Mn ( ⁇ H NMR) is determined according to the NMR method described below in the Examples section. Mn may also be determined using a GPC-DRI method, as described below. For the purpose of the claims, unless indicated otherwise, Mn is determined by !H NMR.
  • the branched polyolefins described herein have an Mw (measured using a GPC-DRI method, as described below) of 1000 g/mol or more (preferably from about 1,000 to about 400,000 g/mol, preferably from about 2000 to 300,000 g/mol, preferably from about 3,000 to 200,000 g/mol) and/or an Mz in the range of from about 1700 to about 150,000 g/mol or preferably from about 800 to 100,000 g/mol, and/or an Mw/Mn in the range of from about 1.2 to 20 (alternately from about 1.7 to 10, alternately from about 1.8 to 5.5).
  • Mw measured using a GPC-DRI method, as described below
  • the branched polyolefins described herein have a ratio of Mn GPCyMn ⁇ H NMR) of 0.95 or less (preferably 0.90 or less, preferably 0.85 or less, preferably 0.80 or less).
  • Figure 1 shows a plot of Mn as determined by GPC versus Mn calculated from NMR data, as shown below.
  • the plot of the best fit line for the experimental data lies below the parity plot (dashed line).
  • the slope of the best fit line is 0.73065.
  • Mn is calculated from NMR data, assuming one unsaturation per polyolefin chain. NMR data is collected at either room temperature or 120°C (for purposes of the claims, 120°C shall be used) in a 5 mm probe using a Varian spectrometer with a proton frequency of 250 MHz, 400 MHz, or 500 MHz (for the purpose of the claims, a proton frequency of 400 mHz is used). Data is recorded using a maximum pulse width of 45°C, 8 seconds between pulses and signal averaging 120 transients. Spectral signals are integrated and the number of unsaturation types per 1000 carbons is calculated by multiplying the different unsaturation groups by 1000 and dividing the result by the total number of carbons. Mn ( i n NMR) is calculated by dividing the total number of unsaturated species into 14,000, and has units of g/mol.
  • Mn, Mw, Mz, carbon number, and g'vis are measured by a GPC-DRI (Gel Permeation Chromatograph-Differential Refractive Index) method using a High Temperature Size Exclusion Chromatograph (SEC, either from Waters Corporation or Polymer Laboratories), equipped with a DRI.
  • GPC-DRI Gel Permeation Chromatograph-Differential Refractive Index
  • SEC High Temperature Size Exclusion Chromatograph
  • Solvent for the SEC experiment is prepared by dissolving 6 grams of butylated hydroxy toluene as an antioxidant in 4 liters of Aldrich reagent grade 1, 2, 4-trichlorobenzene (TCB). The TCB mixture is then filtered through a 0.7 ⁇ glass pre-filter and subsequently through a 0.1 ⁇ Teflon filter. The TCB is then degassed with an online degasser before entering the SEC. Polymer solutions are prepared by placing dry polymer in a glass container, adding the desired amount of TCB, then heating the mixture at 160°C with continuous agitation for about 2 hours.
  • the TCB densities used to express the polymer concentration in mass/volume units are 1.463 g/mL at room temperature and 1.324 g/mL at 135°C.
  • the injection concentration is from 1.0 to 2.0 mg/mL, with lower concentrations being used for higher molecular weight samples.
  • the DRI detector and the injector Prior to running each sample the DRI detector and the injector are purged. Flow rate in the apparatus is then increased to 0.5 mL/minute, and the DRI is allowed to stabilize for 8 to 9 hours before injecting the first sample.
  • the concentration, c, at each point in the chromatogram is calculated from the baseline-subtracted DRI signal, 3 ⁇ 4RJ, using the following equation:
  • K D RJ is a constant determined by calibrating the DRI
  • (dn/dc) is the refractive index increment for the system.
  • (dn/dc) 0.104 for propylene polymers and 0.1 otherwise.
  • concentration is expressed in g/cm 3
  • molecular weight is expressed in g/mol
  • intrinsic viscosity is expressed in dL/g.
  • the LS detector is a Wyatt Technology High Temperature mini-DAW .
  • the molecular weight, M, at each point in the chromatogram is determined by analyzing the LS output using the Zimm model for static light scattering (M.B. Huglin, LIGHT SCATTERING FROM POLYMER SOLUTIONS, Academic Press, 1971):
  • AR(9) is the measured excess Rayleigh scattering intensity at scattering angle ⁇
  • c is the polymer concentration determined from the DRI analysis
  • (dn/dc) 0.104 for propylene polymers, 0.098 for butene polymers and 0.1 otherwise
  • ⁇ ( ⁇ ) is the form factor for a monodisperse random coil
  • K 0 is the optical constant for the system:
  • a high temperature Viscotek Corporation viscometer which has four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers, is used to determine specific viscosity.
  • One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides of the bridge, measures a differential pressure.
  • the specific viscosity, n s for the solution flowing through the viscometer is calculated from their outputs.
  • the intrinsic viscosity, [ ⁇ ], at each point in the chromatogram is calculated from the following equation:
  • the branching index (g' v i s ) is calculated using the output of the SEC-DRI-LS-VIS method as follows.
  • ] aV g, of the sample is calculated by:
  • the branching index g'vis is defined as:
  • M v is the viscosity-average molecular weight based on molecular weights determined by LS analysis. See Macromolecules, 2001, 34, pp. 6812-6820 and Macromolecules, 2005, 38, pp. 7181-7183, for guidance on selecting a linear standard having similar molecular weight and comonomer content, and determining k coefficients and a exponents.
  • the branched polyolefin has 50% or greater allyl chain ends (preferably 60% or more, preferably 70% or more, preferably 80% or more, preferably 90% or more, preferably 95% or more).
  • Branched polyolefins generally have a chain end (or terminus) which is saturated and/or an unsaturated chain end.
  • the unsaturated chain end of the inventive polymers comprises "allyl chain ends.”
  • An allyl chain end is represented by the formula:
  • the "allyl chain end to vinylidene chain end ratio" is defined to be the ratio of the percentage of allyl chain ends to the percentage of vinylidene chain ends. In some embodiments, the allyl chain end to vinylidene chain end ratio is more than 10: 1 (preferably greater than 15: 1).
  • the "allyl chain end to vinylene chain end ratio" is defined to be the ratio of the percentage of allyl chain ends to the percentage of vinylene chain ends. In some embodiments, the allyl chain end to vinylene chain end ratio is greater than 1 : 1 (preferably greater than 2: 1, greater than 5: 1, or greater than 10: 1).
  • the "allyl chain end to internal vinylidene ratio" is defined to be the ratio of the percentage of allyl chain ends to the percentage of internal (or non-terminal) vinylidene groups. In some embodiments, the allyl chain end to internal vinylidene ratio is greater than 5: 1 (preferably greater than 10: 1).
  • the number of allyl chain ends, vinylidene chain ends and vinylene chain ends is determined using NMR at 120°C using deuterated tetrachloroethane as the solvent on an at least 250 MHz NMR spectrometer, and in selected cases, confirmed by 13 C NMR.
  • Allyl chain ends are reported as a molar percentage of the total number of moles of unsaturated groups (that is, the sum of allyl chain ends, vinylidene chain ends, vinylene chain ends, and the like).
  • the unsaturated chain ends may be further characterized by using bromine electrometric titration, as described in ASTM D 1 159.
  • the bromine number obtained is useful as a measure of the unsaturation present in the sample.
  • branched polyolefins have a bromine number which, upon complete hydrogenation, decreases by at least 50% (preferably by at least 75%).
  • the branched polyolefin also has at least one saturated chain end, preferably at least two saturated chain ends, per branched polyolefin molecule.
  • the branched polyolefins produced herein have a ratio of percentage of saturated chain ends (preferably isobutyl chain ends) to percentage of allyl chain ends of 1.2 to 2.0 (preferably 1.6 to 1.8), wherein the percentage of saturated chain ends is determined using 13 C NMR as described in WO 2009/155471 at paragraph [0095] and [0096] except that the spectra are referenced to the chemical shift of the solvent, tetrachloroethane-d2.
  • the saturated chain end which may comprise an isobutyl chain end.
  • An "isobutyl chain end” is defined to be an end or terminus of a polymer, represented as shown in the formula below: isobutyl chain end
  • M represents the polymer chain.
  • the structure of the branched polyolefin near the saturated chain end may differ, depending on the types and amounts of monomer(s) used, and method of insertion during the polymerization process.
  • the branched polyolefins comprise propylene-derived units and C 4 to C 4 Q alpha olefin derived units
  • the structure of the polymer within four carbons of the isobutyl chain end is represented by one of the following formulae:
  • isobutyl chain end isobutyl chain end where M represents the rest of the polymer chain and C m represents the polymerized monomer, each C m may be the same or different, and where m is an integer from 2 to 8.
  • the branched polyolefin has a ratio of percentage of saturated chain ends (preferably isobutyl chain ends) to percentage of allyl chain ends of 1.2 to 2.0 (preferably 1.6 to 1.8), wherein the percentage of saturated chain ends is determined using 13 C NMR as described in WO 2009/155471 at paragraph [0095] and [0096] except that the spectra are referenced to the chemical shift of the solvent, tetrachloroethane-d2.
  • the branched polyolefins described herein have a Tm of greater than 60°C (preferably greater than 100°C, preferably from 60 to 180°C, preferably from 80 to 175°C).
  • the branched polyolefins described herein have an Hf of greater than 7 J/g (preferably greater than 15 J/g, greater than 30 J/g, greater than 50 J/g, greater than 60 J/g, or greater than 80 J/g).
  • the branched polyolefins described herein have a glass transition temperature (Tg) of less than 0°C or less (as determined by differential scanning calorimetry as described below), preferably -10°C or less, more preferably -20°C or less, more preferably -30°C or less, more preferably -50°C or less.
  • Tg glass transition temperature
  • Tm, Hf, and Tg are measured using Differential Scanning Calorimetry (DSC) using commercially available equipment such as a TA Instruments Model Q100.
  • DSC Differential Scanning Calorimetry
  • 6 to 10 mg of the sample, that has been stored at room temperature for at least 48 hours, is sealed in an aluminum pan and loaded into the instrument at room temperature.
  • the sample is equilibrated at 25°C, then it is cooled at a cooling rate of 10°C/min to -80°C.
  • the sample is held at -80°C for 5 min and then heated at a heating rate of 10°C/min to 25°C.
  • the glass transition temperature is measured from the heating cycle.
  • the sample is equilibrated at 25°C for 5 minutes, then heated at a heating rate of 10°C/min to 200°C, followed by an equilibration at 200°C for 5 minutes, and cooled at 10°C/min to -80°C.
  • the endothermic melting transition if present, is analyzed for onset of transition and peak temperature.
  • the melting temperatures reported are the peak melting temperatures from the first heat unless otherwise specified.
  • the melting point (or melting temperature) is defined to be the peak melting temperature associated with the largest endothermic calorimetric response in that range of temperatures from the DSC melting trace.
  • Areas under the DSC curve are used to determine the heat of transition (heat of fusion, Hf, upon melting or heat of crystallization, He, upon crystallization, if the Hf value from the melting is different from the He value obtained for the heat of crystallization, then the value from the melting (Tm) shall be used), which can be used to calculate the degree of crystallinity (also called the percent crystallinity).
  • the percent crystallinity (X%) is calculated using the formula: [area under the curve (in J/g) / H° (in J/g)] * 100, where H° is the heat of fusion for the homopolymer of the major monomer component.
  • H° equilibrium heat of fusion
  • a value of 290 J/g is used as the equilibrium heat of fusion (H°) for 100% crystalline polyethylene
  • a value of 140 J/g is used as the equilibrium heat of fusion (H°) for 100% crystalline polybutene
  • a value of 207 J/g (H°) is used as the heat of fusion for a 100% crystalline polypropylene.
  • any of the branched polyolefins described herein have a viscosity at 190°C of greater than 50 mPa.sec, greater than 100 mPa.sec, or greater than 500 mPa.sec. In other embodiments, the branched polyolefins have a viscosity of less than 15,000 mPa.sec, or less than 10,000 mPa.sec. Viscosity is defined herein as resistance to flow and is measured at an elevated temperature using a Brookfield Viscometer according to ASTM D-3236.
  • any of the branched polyolefins described herein comprises less than 3 wt% of functional groups selected from hydroxide, aryls and substituted aryls, halogens, alkoxys, carboxylates, esters, acrylates, oxygen, nitrogen, and carboxyl (preferably less than 2 wt%, less than 1 wt%, less than 0.5 wt%, less than 0.1 wt%, or 0 wt%), based upon the weight of the copolymer.
  • any of the branched polyolefins described herein comprises at least 50 wt% (preferably at least 75 wt%, preferably at least 90 wt%), based upon the weight of the copolymer composition, of olefins having at least 36 carbon atoms (preferably at least 51 carbon atoms or at least 102 carbon atoms) as measured by NMR, assuming one unsaturation per chain.
  • the branched polyolefins comprise less than 20 wt% dimer and trimer (preferably less than 10 wt%, preferably less than 5 wt%, more preferably less than 2 wt%, based upon the weight of the copolymer composition), as measured by gas chromatography.
  • "Dimer” (and “trimer”) are defined as copolymers having two (or three) monomer units, where the monomer units may be the same or different from each other (where "different” means differing by at least one carbon). Products are analyzed by gas chromatograph (Agilent 6890N with auto-injector) using helium as a carrier gas at 38 cm/sec.
  • a column having a length of 60m (J & W Scientific DB-1, 60 m x 0.25 mm I.D.x 1.0 ⁇ film thickness) packed with a flame ionization detector (FID), an Injector temperature of 250°C, and a Detector temperature of 250°C are used.
  • the sample is injected into the column in an oven at 70°C, then heated to 275°C over 22 minutes (ramp rate 10°C/min to 100°C, 30°C/min to 275°C, hold).
  • An internal standard usually the monomer, is used to derive the amount of dimer or trimer product that is obtained. Yields of dimer and trimer product are calculated from the data recorded on the spectrometer. The amount of dimer or trimer product is calculated from the area under the relevant peak on the GC trace, relative to the internal standard.
  • any of the branched polyolefins described herein contain less than 25 ppm hafnium or zirconium, preferably less than 10 ppm hafnium or zirconium, preferably less than 5 ppm hafnium or zirconium, based on the yield of polymer produced and the mass of catalyst employed.
  • ICPES Inductively Coupled Plasma Emission Spectrometry
  • ICPES Inductively Coupled Plasma Emission Spectrometry
  • the branched polyolefin is a liquid at 25°C.
  • the branched polyolefin may be a homopolymer of propylene.
  • the branched polyolefin may also be a copolymer, a terpolymer, or so on.
  • the branched polyolefin comprises from about 0.1 to 99.9 mol% (preferably from about 5 to about 90 mol%, from about 15 to about 85 mol%, from about 25 to about 80 mol%, from about 35 to about 75 mol%, or from about 45 to about 95 mol%) of propylene.
  • the branched polyolefin comprises greater than 5 mol% (preferably greater than 10 mol%, greater than 20 mol%, greater than 35 mol%, greater than 45 mol%, greater than 55 mol%, greater than 70 mol%, or greater than 85 mol%) of propylene.
  • the branched polyolefin comprises C 4 to C 4 Q monomers, preferably C 4 to C20 monomers, or preferably C 4 to C ⁇ monomers.
  • the C 4 to C 4 Q monomers may be linear or cyclic.
  • the cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include hetero atoms and/or one or more functional groups.
  • Exemplary monomers include butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, cyclopentene, cycloheptene, cyclooctene, cyclododecene, 7-oxanorbornene, substituted derivatives thereof, and isomers thereof, preferably hexane, heptene, octene, nonene, decene, dodecene, cyclooctene, l-hydroxy-4- cyclooctene, l-acetoxy-4-cyclooctene, cyclopentene, norbornene, and their respective homologs and derivatives.
  • the branched polyolefin comprises two or more different C 4 to C 4 o monomers, three or more different C 4 to C 4 Q monomers, or four or more different C 4 to C 4 o monomers.
  • the branched polyolefin comprises from about 0.1 to 99.9 mol% (preferably from about 5 to about 90 mol%, from about 15 to about 85 mol%, from about 25 to about 80 mol%, from about 35 to about 75 mol%, or from about 45 to about 95 mol%) of at least one (preferably two or more, three or more, four or more, and the like) C 4 to C 4 Q (preferably butene, pentene, hexene, heptene, octene, nonene, decene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, and isomers thereof) monomers.
  • the branched polyolefin comprises greater than 5 mol% (preferably greater than 10 mol%, greater than 20 mol%, greater than 35 mol%, greater than 45 mol%, greater than 55 mol%, greater than 70 mol%, or greater than 85 mol%) of C 4 to C 4 Q (preferably butene, pentene, hexene, octene, and decene) monomer.
  • C 4 to C 4 Q preferably butene, pentene, hexene, octene, and decene
  • the branched polyolefins are homopolypropylene, propyl ene/ethylene copolymers, propylene/hexene copolymers, propylene/octene copolymers, propylene/decene copolymers, propylene/hexene/octene terpolymers, propyl ene/hexene/decene terpolymers, propylene/octene/decene terpolymers, and the like.
  • the vinyl terminated branched polymers prepared herein may be functionalized by reacting a heteroatom containing group with the allyl group of the polymer, with or without a catalyst.
  • a heteroatom containing group examples include catalytic hydrosilylation, hydroformylation, hydroboration, epoxidation, hydration, dihydroxylation, hydroamination, or maleation with or without activators such as free radical generators (e.g., peroxides).
  • the vinyl terminated branched polymers produced herein are functionalized as described in U.S. Patent No. 6,022,929; A. Toyota, T. Tsutsui, and N. Kashiwa, Polymer Bulletin 48, pp. 213-219, 2002; J. Am. Chem. Soc, 1990, 1 12, pp. 7433- 7434; and USSN 12/487,739 filed on June 19, 2009 (Published as WO 2009/155472).
  • the functionalized branched polymers can be used in oil additivation and many other applications.
  • Preferred uses include additives for lubricants and/or fuels.
  • Preferred heteroatom containing groups include amines, aldehydes, alcohols, acids, succinic acid, maleic acid, and maleic anhydride.
  • the vinyl terminated branched polymers disclosed herein, or functionalized analogs thereof are useful as additives.
  • the vinyl terminated polymers disclosed herein, or functionalized analogs thereof are useful as additives to a lubricant.
  • Particular embodiments relate to a lubricant comprising the vinyl terminated polymers disclosed herein, or functionalized analogs thereof.
  • the vinyl terminated branched polymers disclosed herein may be used as monomers for the preparation of polymer products. Processes that may be used for the preparation of these polymer products include coordinative polymerization and acid-catalyzed polymerization.
  • the polymeric products may be homopolymers. For example, if a vinyl terminated polymer (A) were used as a monomer, it is possible to form a homopolymer product with the formulation (A) n , where n is the degree of polymerization.
  • the polymer products formed from mixtures of monomer vinyl terminated polymers may be mixed polymers, comprising two or more repeating units that are different from each.
  • a vinyl terminated polymer (A) and a different vinyl terminated polymer (B) were copolymerized, it is possible to form a mixed polymer product with the formulation (A) n (B) m , where n is the number of molar equivalents of vinyl terminated polymer (A) and m is the number of molar equivalents of vinyl terminated polymer (B) that are present in the mixed polymer product.
  • polymer products may be formed from mixtures of the vinyl terminated branched polymer with another alkene.
  • a vinyl terminated branched polymer (A) and alkene (B) were copolymerized, it is possible to form a mixed polymer product with the formulation (A) n (B) m , where n is the number of molar equivalents of vinyl terminated polymer and m is the number of molar equivalents of alkene that are present in the mixed polymer product.
  • this invention relates to a functionalized branched polyolefin comprising the reaction product of a heteroatom containing group and any vinyl terminated branched polyolefin described herein, preferably where the functional group comprises one or more heteroatoms selected from the group consisting of P, O, S, N, Br, CI, F, I, and/or B, and the functionalized branched polyolefin has 0.60 to 1.2, alternately, 0.75 to 1.10, functional groups per chain (preferably assuming that Mn has not altered by more than 15% as compared to the Mn of the vinyl terminated branched polyolefin prior to functionalization and optional derivatization).
  • the number of functional groups per chain is determined by l R NMR as described in WO 2009/155472 (See pages 26 to 27, paragraphs [001 11] to [001 14], including that VDRA is VRDA, which is the normalized integrated signal intensity for the vinylidene resonances between from about 4.65 to 4.85 ppm and the vinylene resonances at from about 5.15 to 5.6 ppm.)
  • Preferred heteroatom containing groups comprise one or more of sulfonates, amines, aldehydes, alcohols, or acids, preferably the heteroatom containing group comprises an epoxide, succinic acid, maleic acid or maleic anhydride, alternately the heteroatom containing group comprises one or more of acids, esters, anhydrides, acid-esters, oxycarbonyls, carbonyls, formyls, formylcarbonyls, hydroxyls, and acetyl halides.
  • Percent functionalization of the branched polyolefin (F * 100)/(F+VI +VE).
  • the number of vinyl groups/1000 carbons (VI*) and number of vinylidene groups/1000 carbons (VE*) for the functionalized branched polyolefin are determined from the NMR spectra of the functionalized polyolefin in the same manner as VI and VE for the unfunctionalized polymer.
  • the percent functionalization of the branched polyolefin is 75% or more, preferably 80% or more, preferably 90% or more, preferably 95% or more.
  • the functionalized polyolefins described herein have the same Mn, and/or Mw and/or Mz as, or up to 15% greater than (preferably up to 10% greater than), as the starting vinyl terminated polyolefins, "same" is defined to mean within 5%.
  • the vinyl terminated branched polyolefins described herein can be use in any process, blend, product, or composition disclosed in WO 2009/155472, which is incorporated by reference herein.
  • the composition is a lubricant blend, an adhesive, or a wax.
  • the invention relates to the use of the composition as a lubricant blend, an adhesive, or a wax.
  • this invention relates to:
  • a process for polymerization comprising:
  • M is selected from the group consisting of zirconium or hafnium (preferably hafnium);
  • each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof, (two X's may form a part of a fused ring or a ring system) (preferably X is a halide or a hydrocarbyl radical having from 1 to 20 carbon atoms, preferably X is chloride or methyl);
  • each R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 is, independently, hydrogen or a substituted or unsubstituted hydrocarbyl group, a heteroatom or heteroatom containing group;
  • any two adjacent R groups may form a fused ring or multicenter fused ring system where the rings may be aromatic, partially saturated or saturated;
  • any of adjacent R 4 , R 5 , and R 6 groups may form a fused ring or multicenter fused ring system where the rings may be aromatic, partially saturated or saturated;
  • T is a bridging group represented by the formula R2 a J, where J is one or more of C, Si, Ge, N or P (preferably J is Si), and each R a is, independently, hydrogen, halogen, Q to C20 hydrocarbyl or a Q to C20 substituted hydrocarbyl, (preferably R a is methyl, ethyl, chloride) provided that at least one R 3 , preferably both, are a substituted or unsubstituted phenyl group, if any of R 1 , R 2 , R 4 , R 5 or R 6 are not hydrogen;
  • each R 1 is, independently, a halide, preferably a fluoride
  • each R 2 is, independently, a halide, a to C20 substituted aromatic hydrocarbyl group or a siloxy group of the formula -0-Si-R a , where R a is a Q to C20 hydrocarbyl or hydrocarbylsilyl group (preferably R2 is a fluoride or a perfluorinated phenyl group);
  • each R 3 is a halide, to C20 substituted aromatic hydrocarbyl group or a siloxy group of the formula -0-Si-R a , where R a is a Ci to C20 hydrocarbyl or hydrocarbylsilyl group (preferably R3 is a fluoride or a perfluorinated aromatic hydrocarbyl group); wherein R2 and R3 can form one or more saturated or unsaturated, substituted or unsubstituted rings (preferably R2 and R3 form a perfluorinated phenyl ring);
  • L is an neutral Lewis base
  • d is 1, 2, or 3;
  • the anion has a molecular weight of greater than 1020 g/mol
  • the bulky activator is at least one of: trimethylammonium tetrakis(perfluoronaphthyl)borate, triethylammonium tetrakis(perfluoronaphthyl)borate, tripropylammonium tetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammonium tetrakis(perfluoronaphthyl)borate, tri(t-butyl)ammonium tetrakis(perfluoronaphthyl)borate, ⁇ , ⁇ -dimethylanilinium tetrakis(perfluoronaphthyl)borate, ⁇ , ⁇ -diethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethyl-(2,4,6- trimethylanilinium) tetrakis(perfluorona
  • productivity is 4500 g/mmol or more (preferably 5000 g/mmol or more, preferably 10,000 g/mmol or more, preferably 50,000 g/mmol or more; alternately the productivity is at least 80,000 g/mmol, preferably at least 150,000 g/mmol, preferably at least 200,000 g/mmol, preferably at least 250,000 g/mmol, preferably at least 300,000 g/mmol).
  • a g'vis of 0.90 or less (preferably 0.85 or less, preferably 0.80 or less) and/or a ratio of percentage of saturated chain ends (preferably isobutyl chain ends) to percentage of allyl chain ends of 1.2 to 2.0 (preferably 1.6 to 1.8), and/or a ratio of Mn(GPC)/ n( 1 H NMR) of 0.95 or less (preferably 0.90 or less, preferably 0.85 or less, preferably 0.80 or less);
  • Tm optionally, a Tm of greater than 60°C (preferably greater than 100°C, preferably from 60 to 180°C, preferably from 80 to 175°C);
  • an Hf of greater than 7 J/g preferably greater than 15 J/g, greater than 30 J/g, greater than 50 J/g, greater than 60 J/g, or greater than 80 J/g;
  • an allyl chain end to vinylene chain end ratio of greater than 1 : 1 (preferably greater than 2: 1, greater than 5: 1, or greater than 10: 1).
  • a Tm of greater than 60°C preferably greater than 100°C, preferably from 60 to 180°C, preferably from 80 to 175°C
  • an Hf of greater than 7 J/g preferably greater than 15 J/g, greater than 30 J/g, greater than 50 J/g, greater than 60 J/g, or greater than 80 J/g
  • Tm optionally, a Tm of greater than 60°C (preferably greater than 100°C, preferably from 60 to 180°C, preferably from 80 to 175°C);
  • an Hf of greater than 7 J/g preferably greater than 15 J/g, greater than 30 J/g, greater than 50 J/g, greater than 60 J/g, or greater than 80 J/g;
  • an allyl chain end to vinylene chain end ratio of greater than 1 : 1 (preferably greater than 2: 1, greater than 5: 1, or greater than 10: 1).
  • a process for polymerization comprising:
  • M is selected from the group consisting of zirconium or hafnium (preferably hafnium);
  • each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof, (two X's may form a part of a fused ring or a ring system) (preferably X is a halide or a hydrocarbyl radical having from 1 to 20 carbon atoms, preferably X is chloride or methyl);
  • each R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 is, independently, hydrogen or a substituted or unsubstituted hydrocarbyl group, a heteroatom or heteroatom containing group;
  • any two adjacent R groups may form a fused ring or multicenter fused ring system where the rings may be aromatic, partially saturated or saturated; and further provided that any of adjacent R 4 , R 5 , and R 6 groups may form a fused ring or multicenter fused ring system where the rings may be aromatic, partially saturated or saturated;
  • T is a bridging group represented by the formula R2 a J, where J is one or more of C, Si, Ge, N or P (preferably J is Si), and each R a is, independently, hydrogen, halogen, Q to C20 hydrocarbyl or a Q to C20 substituted hydrocarbyl, (preferably R a is methyl, ethyl, chloride) provided that at least one R 3 , preferably both, are a substituted or unsubstituted phenyl group, if any of R 1 , R 2 , R 4 , R 5 or R 6 are not hydrogen;
  • Metallocenes A and C were obtained from Albemarle (Baton Rouge, LA) and used without further purification. Metallocene B was synthesized as shown below.
  • Typical dry-box procedures for synthesis of air-sensitive compounds were followed including using dried glassware (90°C, 4 hours) and anhydrous solvents purchased from Sigma Aldrich (St. Louis, MO) which were further dried over 3 A sieves. All reagents were purchased from Sigma-Aldrich (Milwaukee, WI) and used without further purification, unless otherwise noted.
  • the dichloride precursor of Metallocene B ( ⁇ -(3 ⁇ 4) was obtained from Albemarle, and converted to Metallocene B using the following procedure: Under inert atmosphere, in a purged Vacuum AtmospheresTM dry box, 3.02g of ⁇ -(3 ⁇ 4 was dissolved in 150 mL of dried toluene in a 250 mL single neck round-bottom flask. To this 4.0 mL (5eq) of 3.0M methylmagnesium bromide was added dropwise. The solution was heated in an oil bath at 90°C overnight. The mixture was then allowed to cool to room temperature, at which time 10.0 mL of trimethylsilylchloride was added drop-wise.
  • Activators I and III were purchased from Albemarle.
  • Activator II was purchased from Single Site Catalyst.
  • the solvent feed to the reactors was measured by a mass-flow meter.
  • a Pulsa feed pump controlled the solvent flow rate and increased the solvent pressure to the reactors.
  • the compressed, liquefied propylene feed was measured by a mass flow meter and the flow was controlled by a Pulsa feed pump.
  • the solvent and monomers were fed into a manifold first.
  • the mixture of solvent and monomers were then chilled to about -15°C by passing through a chiller prior to feeding into the reactor through a single tube.
  • the collected samples were first air-dried in a hood to evaporate most of the solvent, and then dried in a vacuum oven at a temperature of about 90°C for about 12 hours.
  • the vacuum oven dried samples were weighed to obtain yields.
  • Monomer conversion was calculated basing the polymer yield on the amount of monomers fed into the reactor. All the reactions were carried out at a pressure of about 2.4 MPa/g.
  • Catalysts used in the following examples were rac-dimethylsilyl bisindenyl hafnium dimethyl (Catalyst A), rac-dimethylsily bis(2-methylindenyl)zirconium dimethyl (Catalyst B), and rac-dimethylsilyl bis(2-methyl-4-phenylindenyl) zirconium dimethyl (Catalyst C).
  • the activators used were ⁇ , ⁇ -dimethylanilinium tetrakis(pentafluorophenyl) borate (Activator I), trityl tetrakis(pentafluorophenyl) borate (Activator II), and N,N-dimethyl anilinium tetrakis (heptafluoro-2-naphthyl) borate (Activator III). All of the metallocene catalysts were preactivated with an activator at a molar ratio of about 1 : 1 in 900 ml of toluene. All catalyst solutions were kept in an inert atmosphere and fed into reactors by metering pumps. Tri-n-octylaluminum (TNOAL) solution (available from Sigma Aldrich, Milwaukee, WI) was further diluted in isohexane and used as a scavenger.
  • TNOAL Tri-n-octylaluminum
  • Metallocene C offers excellent melting point capability. Increasing polymerization temperature results in a decrease in melting point. The decrease in melting point is thought to arise from a higher population of stereo- and region- defects in the products. Among the activators, Activator III appears to be the most effective at increasing the melting point.
  • NMR spectra were recorded for most samples.
  • a summary of the concentrations of the olefin unsaturations is provided in Table 4.
  • the number average molecular weight of each sample was calculated from the NMR data assuming one unsaturation per chain, and in Table 4 these values were compared with the number average molecular weights derived from GPC.
  • Mn calculated from NMR is considered reasonably reliable up to about 50,000 g/mol.
  • a parity plot of Mn (it! NMR) versus Mn (GPC-DRI) is shown in Figure 1. In most cases, Mns derived from the two methods are in close agreement, although there are notable exceptions. Departures from parity are thought to be due to contributions from long chain branching.
  • compositions encompasses the terms “consisting essentially of,” “is,” and “consisting of and any place “comprising” is used “consisting essentially of,” “is,” or “consisting of may be substituted therefore.

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Abstract

La présente invention concerne un procédé de polymérisation, comprenant : (i) le contact, à une température supérieure à 35 °C, d'un ou de plusieurs monomères comprenant l'éthylène et/ou le propylène, avec un système catalytique comprenant un catalyseur à base de métallocène et un activateur, (ii) la conversion d'au moins 50 % en mole du monomère en polyoléfine ; et (iii) l'obtention d'une polyoléfine ramifiée contenant plus de 50 % de chaînes terminales allyliques, par rapport à la totalité des chaînes terminales insaturées. L'invention concerne également des polyoléfines ramifiées et des polyoléfines ramifiées fonctionnalisées.
EP20120762766 2011-03-25 2012-03-05 Polymères ramifiés à terminaison vinylique et procédés pour les produire Withdrawn EP2688923A4 (fr)

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PCT/US2012/027675 WO2012134715A2 (fr) 2011-03-25 2012-03-05 Polymères ramifiés à terminaison vinylique et procédés pour les produire

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JP2014508848A (ja) 2014-04-10
EP2688923A4 (fr) 2015-05-20
WO2012134715A3 (fr) 2013-01-17
WO2012134715A2 (fr) 2012-10-04
CN103443137A (zh) 2013-12-11
JP5793820B2 (ja) 2015-10-14

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