WO2012134717A2 - Polymères d'oléfines supérieures à terminaison vinyle et leurs procédés de production - Google Patents

Polymères d'oléfines supérieures à terminaison vinyle et leurs procédés de production Download PDF

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WO2012134717A2
WO2012134717A2 PCT/US2012/027682 US2012027682W WO2012134717A2 WO 2012134717 A2 WO2012134717 A2 WO 2012134717A2 US 2012027682 W US2012027682 W US 2012027682W WO 2012134717 A2 WO2012134717 A2 WO 2012134717A2
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borate
tetrakis
independently
group
mol
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WO2012134717A3 (fr
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Donna J. Crowther
Matthew W. Holtcamp
John R. Hagadorn
Charles J. Ruff
George Rodriguez
Patrick Brant
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ExxonMobil Chemical Patents Inc
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ExxonMobil Chemical Patents Inc
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Priority claimed from US13/072,249 external-priority patent/US8399724B2/en
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Priority to JP2014501091A priority Critical patent/JP5739054B2/ja
Priority to CN201280014747.1A priority patent/CN103443144B/zh
Priority to EP12763904.5A priority patent/EP2688926A4/fr
Publication of WO2012134717A2 publication Critical patent/WO2012134717A2/fr
Publication of WO2012134717A3 publication Critical patent/WO2012134717A3/fr
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • C10M107/10—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation containing aliphatic monomer having more than 4 carbon atoms
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
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    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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    • 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+
    • 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
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65925—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
    • 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
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/06—Metallocene or single site catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/024—Propene
    • C10M2205/0245—Propene used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/026—Butene
    • C10M2205/0265—Butene used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/071—Branched chain compounds
    • C—CHEMISTRY; METALLURGY
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions

Definitions

  • This invention relates to olefin copolymerization, particularly to produce vinyl terminated copolymers.
  • 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 Mn's and do not have at least 93% allylic vinyl unsaturation.
  • Weng et al. discloses materials with up to about 81 percent 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 l H NMR) and a melting point of about 143°C.
  • Macromolecules, 33, 2000, pp. 8541-8548 discloses preparation of branch-block ethylene-butene polymer made by reincorporation of vinyl terminated polyethylene, said branch-block polymer made by a combination of piLxCL ⁇ and (C 5 Me 4 SiMe 2 Ci 2 H 23 )TiCl 2 activated with methylalumoxane.
  • Moscardi et al. (Organometallics, 20, 2001, pg. 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 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.
  • 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 ((Ptff ⁇ 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.
  • This invention relates to higher olefin copolymers having an Mn (measured by X H NMR) of 300 g/mol or greater (preferably 300 to 60,000 g/mol) comprising: (i) from about 20 to 99.9 mol% of at least one C5 to C 4 Q higher olefin; and (ii) from about 0.1 to 80 mol% of propylene; wherein the higher olefin copolymer has at least 40% allyl chain ends.
  • Mn measured by X H NMR
  • This invention relates to higher olefin copolymers having an Mn (measured by X H NMR) of 300 g/mol or greater (preferably 300 to 60,000 g/mol) comprising: (i) from about 80 to 99.9 mol% of at least one C 4 olefin; and (ii) from about 0.1 to 20 mol% of propylene; wherein the higher olefin copolymer has at least 40% allyl chain ends.
  • Mn measured by X H NMR
  • This invention also relates to a process for making higher olefin copolymers, wherein the process comprises contacting, under polymerization conditions: (i) 20 to 99.9 mol% of at least one C 5 to C 4 Q higher olefin; and (ii) 0.1 to 80 mol% of propylene; wherein the contacting occurs in the presence of a catalyst system comprising an activator and at least metallocene compound represented by at least one of the formulae:
  • each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halogens, dienes, amines, phosphines, ethers, and a combination thereof, (two X's may form a part of a fused ring or a ring system); each Q is, independently carbon or a heteroatom; each R 1 is, independently, a Ci to Cg alkyl group, R 1 may the same or different as R 2 ; each R 2 is, independently, a Q to Cg alkyl group; each R 3 is, independently, hydrogen, or a substituted or unsubstituted hydrocarbyl group having from 1 to 8 carbon atoms, provided however that at least three R 3 groups are not hydrogen; each R 4 is, independently, hydrogen or a substituted or unsubstituted hydrocarby
  • 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 8 is, independently, a to alkyl group; each R 9 is, independently, a Q to CIQ alkyl group; each R 10 is hydrogen; each R 1 1 , R 12 , and R 13 , is, independently, hydrogen or a substituted or unsubstituted hydrocarbyl group, a heteroatom or heteroatom containing group; T is a bridging group; and further provided that any of adjacent R 1 1 , R 12 , and R 13 groups may form a fused ring or multicenter fused ring system
  • M is hafnium or zirconium; each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halogens, dienes, amines, phosphines, ethers, or a combination thereof; each R 15 and R 17 are, independently, a to Cg alkyl group; and each R 16 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , and R 28 are, independently, hydrogen, or a substituted or unsubstituted hydrocarbyl group having from 1 to 8 carbon atoms.
  • This invention also relates to a process for making higher olefin copolymers, wherein the process comprises contacting, under polymerization conditions: (i) 80 to 99.9 mol% of at least one C 4 olefin; and (ii) 0.1 to 20 mol% of propylene; wherein the contacting occurs in the presence of a catalyst system comprising an activator and at least one metallocene compound represented by at least one of the formulae:
  • each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halogens, dienes, amines, phosphines, ethers, and a combination thereof, (two X's may form a part of a fused ring or a ring system); each Q is, independently carbon or a heteroatom; each R 1 is, independently, a to Cg alkyl group, R 1 may the same or different as R 2 ; each R 2 is, independently, a Q to Cg alkyl group; each R 3 is, independently, hydrogen, or a substituted or unsubstituted hydrocarbyl group having from 1 to 8 carbon atoms, provided however that at least three R 3 groups are not hydrogen; each R 4 is, independently, hydrogen or a substituted or unsubstituted hydrocarbyl radicals having from 1 to 20 carbon atoms,
  • 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 8 is, independently, a Ci to alkyl group; each R 9 is, independently, a Q to alkyl group; each R 10 is hydrogen; each R 1 1 , R 12 , and R 13 , is, independently, hydrogen or a substituted or unsubstituted hydrocarbyl group, a heteroatom or heteroatom containing group; T is a bridging group (such as R2 a as defined above); and further provided that any of adjacent R 1 1 , R 12 , and R 13 groups may form a fused
  • M is hafnium or zirconium; each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halogens, dienes, amines, phosphines, ethers, or a combination thereof; each R 15 and R 17 are, independently, a to Cg alkyl group; and each R 16 , R 18 , R 19 , R 20 , R21, R22, R23 ; R 24 ; R 25 ; R 26 ; R 27 ; AND R 28 ar6j independently, hydrogen, or a substituted or unsubstituted hydrocarbyl group having from 1 to 8 carbon atoms.
  • This invention even further relates to a composition
  • a composition comprising a higher olefin copolymer having an Mn (measured by NMR) of greater than 200 g/mol comprising: (i) from about 20 to 99.9 mol% of at least one C5 to C40 higher olefin; and (ii) from about 0.1 to 80 mol% of propylene; wherein the higher olefin copolymer has at least 40% allyl chain ends.
  • This invention even further relates to a composition
  • a composition comprising a higher olefin copolymer having an Mn (measured by NMR) of greater than 200 g/mol comprising: (i) from about 80 to 99.9 mol% of at least one C 4 olefin; and (ii) from about 0.1 to 20 mol% of propylene; wherein the higher olefin copolymer has at least 40% allyl chain ends.
  • the invention yet further relates to the use of the compositions disclosed herein as lubricants.
  • Figure 1 is a plot of viscosity as a function of time for representative allyl terminated hexene-propylene copolymers as compared to allyl terminated propylene homopolymers.
  • the inventors have surprisingly discovered a new class of vinyl terminated polymers. Described herein are vinyl terminated higher olefin copolymers, processes to produce such vinyl terminated higher olefin copolymers, and compositions comprising vinyl terminated higher olefin copolymers. These vinyl terminated higher olefin copolymers may find utility as macromonomers for the synthesis of poly(macromonomers), block copolymers, and as additives, for example, as additives to lubricants.
  • the vinyl group of these vinyl terminated copolymers provides a path to functionalization. These functionalized copolymers may be also useful as additives, such as in lubricants.
  • molecular weight means number average molecular weight (Mn), unless otherwise stated.
  • Catalyst activity is a measure of how many grams of polymer (P) are produced using a polymerization catalyst comprising W g of catalyst (cat), over a period of time of T hours; and may be expressed by the following formula: P/(T x W) and expressed in units of gPgcaHhr 1 .
  • Catalyst productivity is a measure of how many grams of polymer (P) are produced using a polymerization catalyst comprising W g of catalyst (cat), over a period of time of T hours; and may be expressed by the following formula: P/(T x W) and expressed in units of gPgcat ⁇ hr "1 . 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.
  • 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.
  • Higher olefin means C 4 to C 4 Q olefins; preferably C 5 to C30 a- olefins; more preferably C5-C20 a-olefins; or even more preferably, C5-Q2 a-olefins.
  • a "higher olefin copolymer” is a polymer comprising two or more different monomer units (where different means the monomer units differ by at least one atom), at least one of which is a higher olefin monomer unit.
  • Mn is number average molecular weight (measured by l R NMR, unless stated otherwise), Mw is weight average molecular weight (measured by Gel Permeation Chromatography, GPC), and Mz is z average molecular weight (measured by GPC), wt% is weight percent, mol% is mole percent, vol% is volume percent and mol is mole.
  • Molecular weight distribution (MWD) is defined to be Mw (measured by GPC) divided by Mn (measured by GPC), Mw/Mn. Unless otherwise noted, all molecular weights (e.g., Mw, Mn, Mz) have units of g/mol.
  • the vinyl terminated higher olefin (VT-HO) copolymers described herein have an Mn (measured by NMR) of greater than 200 g/mol (preferably 300 to 60,000 g/mol, 400 to 50,000 g/mol, 500 to 35,000 g/mol, 300 to 15,000 g/mol, 400 to 12,000 g/mol, or 750 to 10,000 g/mol), and comprise: (i) from about 20 to 99.9 mol% (preferably from about 25 to about 90 mol%, from about 30 to about 85 mol%, from about 35 to about 80 mol%, from about 40 to about 75 mol%, or from about 50 to about 95 mol%) of at least one C 5 to C 4 Q (preferably C ⁇ to C20) higher olefin; and (ii) from about 0.
  • Mn measured by NMR
  • VT-HO copolymer has at least 40% allyl chain ends (preferably at least 50% allyl chain ends, at least 60% allyl chain ends, at least 70% allyl chain ends, or at least 80% allyl chain ends, at least 90% allyl chain ends, at least 95% allyl chain ends) relative to total unsaturation; and, optionally, an isobutyl chain end to allyl chain end ratio of less than 0.70: 1, less than 0.65: 1, less than 0.60: 1, less than 0.50: 1, or less than 0.25: 1, and further optionally, an allyl chain end to vinylidene chain end ratio of greater than 2 : 1 (preferably greater than 2.5 : 1 , greater than 3 : 1, greater than 5 : 1 , or greater
  • the higher olefin copolymer has an Mn of 300 g/mol or more (measured by 1H NMR, preferably 300 to 60,000 g/mol, 400 to 50,000 g/mol, 500 to 35,000 g/mol, 300 to 15,000 g/mol, 400 to 12,000 g/mol, or 750 to 10,000 g/mol), and comprises:
  • the higher olefin copolymer has at least 40% allyl chain ends (preferably at least 50% allyl chain ends, at least 60% allyl chain ends, at least 70% allyl chain ends, or at least 80% allyl chain ends, at least 90% allyl chain ends, at least 95% allyl chain ends) relative to total unsaturation, and in some embodiments, an isobutyl chain end to allyl chain end ratio of less than 0.70: 1, less than 0.65: 1, less than 0.60: 1, less than 0.50: 1, or less than 0.25: 1, and in further embodiments, an allyl chain end to vinylidene group ratio of more than 2: 1, more than 2.5: 1, more than 3 : 1, more than 5: 1, or more than 10: 1.
  • allyl chain ends preferably at least 50% allyl chain ends, at least 60% allyl chain ends, at least 70% allyl chain ends, or at least 80% allyl chain ends, at least 90% allyl chain ends, at least 95% allyl chain ends
  • the VT-HO polymer may be a copolymer, a terpolymer, or so on.
  • VT-HO copolymers generally have a saturated chain end (or terminus) and/or an unsaturated chain end, or terminus.
  • the unsaturated chain end of the inventive copolymers comprises the "allyl chain end.”
  • An allyl chain end is represented by CH ⁇ CH-CH ⁇ ., as shown in formula:
  • 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 a at least 250 MHz NMR spectrometer, and in selected cases, confirmed by 13 C NMR.
  • any of the vinyl terminated polyolefins described or useful herein have 3-alkyl vinyl end groups (where the alkyl is a Q to C38 alkyl), also referred to as a "3-alkyl chain ends" or a "3-alkyl vinyl termination", represented by the formula:
  • R b is a Ci to C1 ⁇ 2 alkyl group, preferably a Ci to C 20 alkyl group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, docecyl, and the like.
  • the amount of 3-alkyl chain ends is determined using 13 C NMR as set out below.
  • any of the vinyl terminated polyolefins described or useful herein have at least 5% 3-alkyl chain ends (preferably at least 10% 3-alkyl chain ends, at least 20% 3-alkyl chain ends, at least 30% 3-alkyl chain ends; at least 40% 3-alkyl chain ends, at least 50% 3-alkyl chain ends, at least 60% 3-alkyl chain ends, at least 70% 3-alkyl chain ends; at least 80% 3-alkyl chain ends, at least 90% 3-alkyl chain ends; at least 95% 3- alkyl chain ends, relative to total unsaturations.
  • any of the vinyl terminated polyolefins described or useful herein have at least 5% 3-alkyl + allyl chain ends, (e.g., all 3-alkyl chain ends plus all allyl chain ends), preferably at least 10% 3-alkyl + allyl chain ends, at least 20% 3-alkyl + allyl chain ends, at least 30% 3-alkyl + allyl chain ends; at least 40% 3-alkyl + allyl chain ends, at least 50% 3-alkyl + allyl chain ends, at least 60% 3-alkyl + allyl chain ends, at least 70% 3-alkyl + allyl chain ends; at least 80% 3-alkyl + allyl chain ends, at least 90% 3-alkyl + allyl chain ends; at least 95% 3-alkyl + allyl chain ends, relative to total unsaturations.
  • 3-alkyl + allyl chain ends e.g., all 3-alkyl chain ends plus all allyl chain ends
  • at least 10% 3-alkyl + allyl chain ends at least
  • the VT-HO copolymer has at least 40% allyl chain ends (at least 50% allyl chain ends, at least 60% allyl chain ends, at least 70% allyl chain ends, at least 80% allyl chain ends, at least 90% allyl chain ends, or at least 95% allyl chain ends).
  • any of the vinyl terminated polyolefins described or useful herein have 3-alkyl vinyl end groups (where the alkyl is a Q to C38 alkyl), also referred to as "3-alkyl chain ends" or "3-alkyl vinyl terminations,” represented by the formula:
  • R b is a to C38 alkyl group, preferably a Ci to C20 alkyl group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, docecyl, and the like.
  • the number of 3-alkyl chain ends is determined using 13 C NMR as set out below.
  • any of the vinyl terminated polyolefins described or useful herein have at least 5% 3-alkyl chain ends (preferably at least 10% 3-alkyl chain ends, at least 20% 3-alkyl chain ends, at least 30% 3-alkyl chain ends; at least 40% 3-alkyl chain ends, at least 50% 3-alkyl chain ends, at least 60% 3-alkyl chain ends, at least 70% 3-alkyl chain ends; at least 80% 3-alkyl chain ends, at least 90% 3-alkyl chain ends; at least 95% 3- alkyl chain ends, relative to total unsaturations.
  • any of the vinyl terminated polyolefins described or useful herein have at least 5% 3-alkyl + allyl chain ends, (e.g., all 3-alkyl chain ends plus all allyl chain ends), preferably at least 10% 3-alkyl + allyl chain ends, at least 20% 3-alkyl + allyl chain ends, at least 30% 3-alkyl + allyl chain ends; at least 40% 3-alkyl + allyl chain ends, at least 50% 3-alkyl + allyl chain ends, at least 60% 3-alkyl + allyl chain ends, at least 70% 3-alkyl + allyl chain ends; at least 80% 3-alkyl + allyl chain ends, at least 90% 3-alkyl + allyl chain ends; at least 95% 3-alkyl + allyl chain ends, relative to total unsaturations.
  • 3-alkyl + allyl chain ends e.g., all 3-alkyl chain ends plus all allyl chain ends
  • at least 10% 3-alkyl + allyl chain ends at least
  • 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.
  • the allyl chain end to vinylidene chain end ratio is more than 2: 1 (preferably more than 2.5: 1, more than 3: 1, more than 5: 1, or more than 10: 1).
  • the allyl chain end to vinylidene chain end ratio is in the range of from about 10: 1 to about 2: 1 (preferably from about 5: 1 to about 2: 1 or from 10: 1 to about 2.5: 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 ratio is greater than 1 : 1 (preferably greater than 2: 1, or greater than 5: 1).
  • VT-HO copolymers also have a saturated chain end which may comprise an isobutyl chain end or a higher olefin chain end.
  • the polymer chain may initiate growth in a propylene monomer, thereby generating an isobutyl chain saturated chain end.
  • the polymer chain may initiate growth in a higher olefin monomer, generating a higher olefin chain saturated end.
  • isobutyl chain end is defined to be an end or terminus of a polymer, represented as shown in the formula below:
  • a "higher olefin chain end” is defined to be an end or terminus of a polymer, represented as shown in the formula below:
  • M represents the polymer chain and n is an integer selected from 4 to 40.
  • the structure of the copolymer 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 structure of the polymer within four carbons of the isobutyl chain end is represented by one of the following formulae:
  • isobutyl chain enc isobutyl chain end where M represents the rest of the polymer chain and C m represents the polymerized higher olefin monomer, each C m may be the same or different, and where m is an integer from 2 to 38.
  • the "isobutyl chain end to allyl chain end ratio" is defined to be the ratio of the percentage of isobutyl chain ends to the percentage of allyl chain ends.
  • the isobutyl chain end to allyl chain end is less than 0.70: 1 (preferably less than 0.65: 1, less than 0.60: 1, less than 0.50: 1, or less than 0.25: 1).
  • the isobutyl chain end to allyl chain end ratio is in the range of from about 0.01 : 1 to about 0.70: 1 (preferably from about 0.05: 1 to about 0.65: 1 or from 0.1 : 1 to about 0.60: 1).
  • the VT-HO copolymer preferably has a Mn, as determined by l R NMR, of 300 g/mol or more (preferably from about 300 to 60,000 g/mol, 400 to 50,000 g/mol, preferably 500 to 35,000 g/mol, preferably 300 to 15,000 g/mol, preferably 400 to 12,000 g/mol, or preferably 750 to 10,000 g/mol).
  • a desirable molecular weight range can be any combination of any upper molecular weight limit with any lower molecular weight limit described above.
  • Mn is number average molecular weight (measured by l R NMR, unless stated otherwise), Mw is weight average molecular weight (measured by Gel Permeation Chromatography, GPC), and Mz is z average molecular weight (measured by GPC), and molecular weight distribution (MWD, Mw/Mn) is defined to be Mw (measured by GPC) divided by Mn (measured by GPC).
  • Mn ( l 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, Mn is determined by 3 ⁇ 4 NMR.
  • the VT-HO copolymers described herein have a Mw (measured using a GPC-DRI method, as described below) of 1,000 g/mol or more (preferably from about 1,000 to about 400,000 g/mol, preferably from about 2,000 to 300,000 g/mol, preferably from about 3,000 to 200,000 g/mol) and/or a Mz in the range of from about 1,700 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 VT-HO copolymer has a Mn of 300 g/mol or more (preferably from about 300 to about 60,000 g/mol, from about 400 to about 50,000 g/mol, from about 500 to about 35,000 g/mol, from about 300 to about 15,000 g/mol, from about 400 to about 12,000 g/mol, or from about 750 to about 10,000 g/mol), a Mw of 1,000 or more (preferably from about 1,000 to about 400,000 g/mol, from about 2,000 to 300,000 g/mol, or from about 3,000 to 200,000 g/mol), and a Mz of from about 1,700 to about 150,000 g/mol or preferably from about 800 to 100,000 g/mol.
  • Mn 300 g/mol or more (preferably from about 300 to about 60,000 g/mol, from about 400 to about 50,000 g/mol, from about 500 to about 35,000 g/mol, from about 300 to about 15,000 g/mol, from about 400 to about 12,000 g/mol, or from about 750
  • Mn, Mw, and Mz are measured by a GPC-DRI method using a High Temperature Size Exclusion Chromatograph (SEC (a type of Gel Permeation Chromatography, GPC), either from Waters Corporation or Polymer Laboratories), equipped with a differential refractive index detector (DRI).
  • SEC High Temperature Size Exclusion Chromatograph
  • DRI differential refractive index detector
  • 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 VT-HO copolymer comprises from about 20 to about 99.9 mol% (preferably from about 25 to about 90 mol%, from about 30 to about 85 mol%, from about 35 to about 80 mol%, from about 40 to about 75 mol%, or from about 50 to about 95 mol%) of at least one (preferably two or more, three or more, four or more, and the like) C 5 to C40 (preferably C 5 to C30, to C20, or Cg to C ⁇ ) higher olefin monomers.
  • C 5 to C40 preferably C 5 to C30, to C20, or Cg to C ⁇
  • the VT-HO copolymer comprises greater than 20 mol% (preferably greater than 30 mol%, greater than 40 mol%, greater than 45 mol%, greater than 50 mol%, greater than 65 mol%, greater than 75 mol%, or greater than 85 mol%) of C5 to C40 (preferably C5 to C30, C ⁇ to C20, or Cg to C ⁇ ) higher olefin monomer.
  • the VT-HO copolymer comprises less than 99.9 mol% (preferably less than 85 mol%, less than 75 mol%, less than 65 mol%, less than 50 mol%, less than 35 mol%, or less than 25 mol%) of C 5 to C40 higher olefin monomer.
  • the VT-HO copolymer comprises from about 0.1 to about 80 mol% of propylene (preferably from about 5 mol% to about 70 mol%, from about 10 to about 65 mol%, from about 15 to about 55 mol%, from about 25 to about 50 mol%, or from about 30 to about 80 mol%). In other embodiments, the VT-HO copolymer comprises greater than 5 mol% of propylene (preferably greater than 10 mol%, greater than 20 mol%, greater than 35 mol%, greater than 50 mol%, greater than 65 mol%, or greater than 75 mol%).
  • the VT-HO copolymer comprises less than 80 mol% of propylene (preferably less than 75 mol%, less than 70 mol%, less than 65 mol%, less than 50 mol%, less than 35 mol%, less than 20 mol%, or less than 10 mol%).
  • VT-HO copolymers herein comprise at least one C 5 to C 4 Q higher olefin and propylene.
  • the VT-HO copolymers comprise two or more different C5 to C 4 o higher olefin monomers, three or more C5 to C 4 Q different higher olefin monomers, or four or more different C5 to C 4 Q higher olefin monomer.
  • the VT- HO copolymer also comprises ethylene and/or butene.
  • the higher olefin copolymer has an Mn of 300 g/mol or more, preferably 300 to 60,000 g/mol (measured by NMR) and comprises: (i) from about 80 to about 99.9 mol% of at least one C 4 olefin (preferably about 85 to about 99.9 mol%, more preferably about 90 to about 99.9 mol%); and (ii) from about 0.1 to about 20 mol% of propylene (preferably about 0.1 to about 15 mol% or about 0.1 to about 10 mol%); wherein the higher olefin copolymer has at least 40% allyl chain ends (preferably at least 50% allyl chain ends, at least 60% allyl chain ends, at least 70% allyl chain ends, or at least 80% allyl chain ends); and, in some embodiments, an isobutyl chain end to allyl chain end ratio of less than 0.70: 1 (preferably less than 0.65: 1,
  • the VT-HO copolymer 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.
  • 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.
  • the VT-HO copolymer 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 VT-HO copolymer comprises 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 GC.
  • "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 were analyzed by GC (Agilent 6890N with auto-injector) using helium as a carrier gas at 38 cm/sec.
  • a column having a length of 60 m (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 were used.
  • the sample was 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.
  • the VT-HO copolymer contains 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 VT-HO copolymer is a liquid at 25°C.
  • the VT-HO copolymers described herein have a melting temperature (T m , DSC first melt) in the range of from 60 to 130°C, alternately 50 to 100°C.
  • the copolymers described herein have no detectable melting temperature by DSC following storage at ambient temperature (23°C) for at least 48 hours.
  • the VT-HO copolymer preferably has 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.
  • T m and Tg are measured using Differential Scanning Calorimetry (DSC) using commercially available equipment such as a TA Instruments 2920 DSC.
  • DSC Differential Scanning Calorimetry
  • 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, then heated at a heating rate of 10°C/min to 150°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 is defined to be the peak melting temperature (i.e., associated with the largest endothermic calorimetric response in that range of temperatures) from the DSC melting trace.
  • the VT-HO copolymers described herein have a viscosity at 60°C of greater than 1,000 cP, greater than 12,000 cP, or greater than 100,000 cP. In other embodiments, the VT-HO copolymers have a viscosity of less than 200,000 cP, less than 150,000 cP, or less than 100,000 cP. Viscosity is defined as resistance to flow is measured at an elevated temperature using a Brookfield Viscometer.
  • the VT-HO polymers are propylene/hexene copolymers, propylene/octene copolymers, propylene/ decene copolymers, propylene/dodecene copolymers, propylene/hexene/octene terpolymers, propylene/hexene/decene terpolymers, propyl ene/hexene/dodecene terpolymers, propylene/octene/decene terpolymers, propyl ene/octene/dodecene terpolymers, propylene/decene/dodecene terpolymers, and the like.
  • the vinyl terminated 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 with the allyl group of the polymer, with or without a catalyst.
  • 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 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, 112, pp. 7433- 7434; and USSN 12/487,739, filed on June 19, 2009.
  • the functionalized 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 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 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 polymer with another alkene.
  • a vinyl terminated 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.
  • the invention relates to a composition
  • VT-HO copolymers having an Mn of 300 g/mol or more, preferably of 300 to 60,000 g/mol (measured by l K NMR), 400 to 50,000 g/mol, preferably 500 to 35,000 g/mol, preferably 300 to 15,000 g/mol, preferably 400 to 12,000 g/mol, or preferably 750 to 10,000 g/mol, comprising: (i) from about 20 to 99.9 mol% of at least one C 5 to C 4 Q higher olefin, from about 25 to about 90 mol%, from about 30 to about 85 mol%, from about 35 to about 80 mol%, from about 40 to about 75 mol%, or from about 50 to about 95 mol%; and (ii) from about 0.1 to about 80 mol% of propylene, from about 5 mol% to about 70 mol%, from about 10 to about 65 mol%, from about 15 to about 55 mol%, from
  • the invention relates to the use of a composition comprising VT-HO copolymers having an Mn of 300 g/mol or more, preferably 300 to 60,000 g/mol (measured by l R NMR) and comprises: (i) from about 80 to about 99.9 mol% of at least one C 4 olefin, preferably about 85 to about 99.9 mol%, more preferably about 90 to about 99.9 mol%; and (ii) from about 0.1 to about 20 mol% of propylene, preferably about 0.1 to about 15 mol%, more preferably about 0.1 to about 10 mol%; wherein the higher olefin copolymer has at least 40% allyl chain ends, preferably at least 50% allyl chain ends, preferably at least 60% allyl chain ends, preferably at least 70% allyl chain ends, or preferably at least 80% allyl chain ends; in some embodiments, an isobutyl chain end to allyl chain end ratio of less
  • the composition is a lubricant blend.
  • the invention relates to the use of the composition as a lubricant blend.
  • This invention also relates to a process for making higher olefin copolymers, wherein the process comprises contacting, at a temperature of from 0 to 250°C, (preferably 35 to 150°C, preferably from 40 to 120°C, preferably from 45 to 80°C): (i) from about 20 to about 99.9 mol% of at least one C 5 to C 4 Q higher olefin (preferably from about 25 to about 90 mol%, from about 30 to about 85 mol%, from about 35 to about 80 mol%, from about 40 to about 75 mol%, or from about 50 to about 95 mol%); and (ii) from about 0.1 to about 80 mol% of propylene (preferably from about 5 mol% to about 70 mol%, from about 10 to about 65 mol%, from about 15 to about 55 mol%, from about 25 to about 50 mol%, or from about 30 to about 80 mol%); wherein the contacting occurs in the presence of a catalyst system comprising an activator and
  • each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halogens, dienes, amines, phosphines, ethers, and a combination thereof, (two X's may form a part of a fused ring or a ring system); each Q is, independently carbon or a heteroatom; each R 1 is, independently, a Q to Cg alkyl group, R 1 may the same or different as R 2 ; each R 2 is, independently, a Q to Cg alkyl group; each R 3 is, independently, hydrogen, or a substituted or unsubstituted hydrocarbyl group having from 1 to 8 carbon atoms, provided however that at least three R 3 groups are not hydrogen; each R 4 is, independently, hydrogen or a substituted or unsubstituted hydrocarbyl group having from 1 to 8 carbon atoms,
  • 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 8 is, independently, a ⁇ to (3 ⁇ 4 alkyl group; each R 9 is, independently, a Q to alkyl group; each R 10 is hydrogen; each R 1 1 , R 12 , and R 13 , is, independently, hydrogen or a substituted or unsubstituted hydrocarbyl group, a heteroatom or heteroatom containing group; T is a bridging group (such as R2 a as described above); and further provided that any of adjacent R 1 1 , R 12 , and R 13 groups may form
  • M is hafnium or zirconium; each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halogens, dienes, amines, phosphines, ethers, or a combination thereof; each R 15 and R 17 are, independently, a C to Cg alkyl group; and each R 16 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , and R 28 are, independently, hydrogen, or a substituted or unsubstituted hydrocarbyl group having from 1 to 8 carbon atoms.
  • This invention also relates to a process for making higher olefin copolymers, wherein the process comprises contacting, under polymerization conditions: (i) from about 80 to about 99.9 mol% of at least one C 4 olefin, preferably about 85 to about 99.9 mol%, more preferably about 90 to about 99.9 mol%; and (ii) from about 0.1 to about 20 mol% of propylene, preferably about 0.1 to 15 about mol%, more preferably about 0.1 to about 10 mol%; wherein the contacting occurs in the presence of a catalyst system comprising an activator and at least one metallocene compound represented by at least one of the formulae: LA II;
  • each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halogens, dienes, amines, phosphines, ethers, and a combination thereof, (two X's may form a part of a fused ring or a ring system); each Q is, independently carbon or a heteroatom; each R 1 is, independently, a C to Cg alkyl group, R 1 may the same or different as R 2 ; each R 2 is, independently, a C to Cg alkyl group; each R 3 is, independently, hydrogen or a substituted or unsubstituted hydrocarbyl group having from 1 to 8 carbon atoms, provided however that at least three R 3 groups are not hydrogen; each R 4 is, independently, hydrogen or a substituted or unsubstituted hydrocarbyl radicals having from 1 to 20 carbon atoms,
  • 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 8 is, independently, a to alkyl group; each R 9 is, independently, a Q to CIQ alkyl group; each R 10 is hydrogen; each R 1 1 , R 12 , and R 13 , is, independently, hydrogen or a substituted or unsubstituted hydrocarbyl group, a heteroatom or heteroatom containing group; T is a bridging group (such as R2 a as described above); and further provided that any of adjacent R 1 1 , R 12 , and R 13 groups may form a fused
  • M is hafnium or zirconium; each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halogens, dienes, amines, phosphines, ethers, or a combination thereof; each R 15 and R 17 are, independently, a C to Cg alkyl group; and each R 16 , R 18 , R!9, R20 ; R21 ; R 22 ; R 23 ; R 24 ; R 25 ; R 26 ; R 27 ; an d R 28 arej independently, hydrogen, or a substituted or unsubstituted hydrocarbyl group having from 1 to 8 carbon atoms.
  • propylene and higher olefin monomers may be copolymerized by contacting: (i) one or more higher olefin monomer(s); and (ii) propylene monomer; wherein the contacting occurs in the presence of a catalyst system (comprising one or more metallocene compounds, and one or more activators, described below).
  • a catalyst system comprising one or more metallocene compounds, and one or more activators, described below.
  • Other additives may also be used, as desired, such as one or more scavengers, promoters, modifiers, reducing agents, oxidizing agents, hydrogen, aluminum alkyls, or silanes.
  • 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 .
  • Higher olefin monomers useful herein are C 4 to C 4 Q olefins, preferably C 5 to C30 olefins, preferably to C20 olefins, or preferably Cg to (3 ⁇ 4 olefins.
  • 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.
  • the higher olefin monomers may be linear or cyclic.
  • the higher olefin cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include hetero atoms and/or one or more functional groups.
  • Exemplary higher olefin 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 hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, l-hydroxy-4-cyclooctene, l-acetoxy-4-cyclooctene, cyclopentene, norbornene, and their respective homologs and derivatives.
  • 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 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).
  • 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); perhalogenated hydrocarbons such as perfluorinated C4 0 alkanes, chlorobenzene, and aromatic and alkylsubstituted aromatic compounds such as benzene, toluene, mesitylene, and xylene.
  • straight and branched-chain hydrocarbons such as isobutane, butane
  • Suitable solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-l-pentene, 4-methyl- 1-pentene, 1-octene, 1-decene, and mixtures thereof.
  • aliphatic hydrocarbon solvents 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 productivity is 4,500 g/mmol/hour or more, preferably 5,000 g/mmol/hour or more, preferably 10,000 g/mmol/hr or more, preferably 50,000 g/mmol/hr or more. In other embodiments, the productivity is at least 80,000 g/mmol/hr, preferably at least 150,000 g/mmol/hr, preferably at least 200,000 g/mmol/hr, preferably at least 250,000 g/mmol/hr, preferably at least 300,000 g/mmol/hr.
  • the activity of the catalyst is at least 50 g/mmol/hour, preferably 500 or more g/mmol/hour, preferably 5,000 or more g/mmol/hr, preferably 50,000 or more g/mmol/hr.
  • the conversion of olefin monomer is at least 10%, based upon polymer yield and the weight of the monomer entering the reaction zone, preferably 20% or more, preferably 30% or more, preferably 50% or more, preferably 80% or more.
  • Preferred polymerizations can be run at any temperature and/or pressure suitable to obtain the desired VT-HO copolymers.
  • Typical temperatures and/or pressures such as at a temperature in the range of from about 0°C to 250°C (preferably 35°C to 150°C, from 40°C to 120°C, from 45°C to 80°C); and at 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 run time of the reaction is up to 300 minutes, preferably in the range of from about 5 to 250 minutes, or preferably from about 10 to 120 minutes.
  • 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), and 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), and 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 less than 0.5 wt%, preferably
  • 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); and 8) optionally 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)).
  • the catalyst system used in the polymerization comprises no more than one catalyst compound.
  • reaction zone also referred to as a "polymerization zone” is a vessel where polymerization takes place, for example a batch reactor.
  • each reactor is considered as a separate polymerization zone.
  • each polymerization stage is considered as a separate polymerization zone.
  • the polymerization occurs in one reaction zone. Room temperature is 23 °C unless otherwise noted.
  • the invention relates to a process for making higher olefin copolymers, wherein the process comprises contacting the propylene and higher olefin monomers in the presence of a catalyst system comprising an activator and at least one metallocene compound, as shown below.
  • the metallocene catalyst may be described as a catalyst precursor, a pre-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 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.
  • 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
  • a "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 C ⁇ to 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 component of the catalyst system is represented by at least one of the formulae I, II, III, IV, V, or VI.
  • the metallocene compound is represented by at least one of
  • M is hafnium or zirconium
  • each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halogens, dienes, amines, phosphines, ethers, or a combination thereof; preferably methyl, ethyl, propyl, butyl, phenyl, benzyl, chloride, bromide, iodide, (alternately two X's may form a part of a fused ring or a ring system);
  • each Q is, independently carbon or a heteroatom, preferably C, N, P, S (preferably at least one Q is a heteroatom, alternately at least two Q's are the same or different heteroatoms, alternately at least three Q's are the same or different heteroatoms, alternately at least four Q's are the same or different heteroatoms);
  • each R 1 is, independently, hydrogen or a Q to Cg alkyl group, preferably a Q to Cg linear alkyl group, preferably methyl ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, R 1 may the same or different as R 2 ;
  • each R 2 is, independently, hydrogen or a to Cg alkyl group, preferably a Q to Cg linear alkyl group, preferably methyl ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, provided that at least one of R 1 or R 2 is not hydrogen, preferably both of R 1 and R 2 are not hydrogen, preferably R 1 and/or R 2 are not branched;
  • each R 3 is, independently, hydrogen, or a substituted or unsubstituted hydrocarbyl group having from 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, preferably a substituted or unsubstituted Q to Cg linear alkyl group, preferably methyl ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, provided however that at least three R 3 groups are not hydrogen (alternately four R 3 groups are not hydrogen, alternately five R 3 groups are not hydrogen); each R 4 is, independently, hydrogen or a substituted or unsubstituted hydrocarbyl group, a heteroatom or heteroatom containing group, preferably a substituted or unsubstituted hydrocarbyl group having from 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, preferably a substituted or unsubstituted Q to Cg linear alkyl group, preferably methyl ethyl,
  • R 5 is hydrogen or a to Cg alkyl group, preferably a Q to Cg linear alkyl group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl;
  • R 6 is hydrogen or a Ci to Cg alkyl group, preferably a Q to Cg linear alkyl group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl;
  • each R 7 is, independently, hydrogen or a C ⁇ to Cg alkyl group, preferably a Q to Cg linear alkyl group, preferably methyl ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, provided however that at least seven R 7 groups are not hydrogen, alternately at least eight R 7 groups are not hydrogen, alternately all R 7 groups are not hydrogen, (preferably the R 7 groups at the 3 and 4 positions on each Cp ring of Formula IV are not hydrogen);
  • R2 a T is a bridging group, preferably T is C, Si or Ge, preferably Si;
  • each R a is independently, hydrogen, halogen or a C to C20 hydrocarbyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl, benzyl, substituted phenyl, and two R a can form a cyclic structure including aromatic, partially saturated, or saturated cyclic or fused ring system; and
  • 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.
  • At least one R 4 group is not hydrogen, alternately at least two R 4 groups are not hydrogen, alternately at least three R 4 groups are not hydrogen, alternately at least four R 4 groups are not hydrogen, alternately all R 4 groups are not hydrogen.
  • the bridging group R2 a includes bridging groups containing at least one Group 13 to 16 atom, often referred to as a divalent moiety, such as, but not limited to, at least one of a carbon, oxygen, nitrogen, silicon, aluminum, boron, germanium and tin atom, or a combination thereof.
  • bridging group T contains a carbon, silicon or germanium atom, most preferably, T contains at least one silicon atom or at least one carbon atom.
  • the bridging group T may also contain substituent groups R* as defined below including halogens and iron.
  • Non- limiting examples of substituent groups R* include one or more from the group selected from hydrogen, or linear, or branched alkyl radicals, alkenyl radicals, alkenyl radicals, cycloalkyl radicals, aryl radicals, acyl radicals, aryl radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl- or dialkyl- carbamoyl radicals, acyloxy radicals, acylamino radicals, arylamino radicals or combination thereof.
  • substituent groups R* have up to 50 non-hydrogen atoms, preferably from 1 to 30 carbon, that may also be substituted with halogens or heteroatoms or the like.
  • alkyl substituents R* include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl groups and the like, including all their isomers, for example tertiary butyl, isopropyl, and the like.
  • hydrocarbyl radicals include fluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbyl substituted organometalloid radicals including trimethylsilyl, trimethylgermyl, methyldiethylsilyl and the like; and halocarbyl-substituted organometalloid radicals including tris(trifluoromethyl)silyl, methyl-bis(difluoromethyl)silyl, bromomethyldimethylgermyl and the like; and disubstituted boron radicals including dimethylboron for example; and disubstituted pnictogen radicals including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine, chalcogen radicals including methoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethylsulfide
  • Non-hydrogen substituents R* include the atoms carbon, silicon, boron, aluminum, nitrogen, phosphorous, oxygen, tin, sulfur, germanium and the like, including olefins, such as, but not limited to, olefinically unsaturated substituents including vinyl-terminated ligands, for example, but-3-enyl, prop-2-enyl, hex-5- enyl and the like. Also, in some embodiments, at least two R* groups, preferably two adjacent R groups, are joined to form a ring structure having from 3 to 30 atoms selected from carbon, nitrogen, oxygen, phosphorous, silicon, germanium, aluminum, boron or a combination thereof.
  • R* may also be a diradical bonded to L at one end and forming a carbon sigma bond to the metal M.
  • R* substituent groups include a Q to C30 hydrocarbyl, a heteroatom or heteroatom containing group (preferably 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.
  • the bridging group 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, silylcyclobutyl (Si(CH 2 ) 3 , (Ph) 2 C, (p-(Et) 3 SiPh) 2 C and silylcyclopentyl (Si(CH 2 ) 4 ).
  • the bridging group is selected from CH 2 , CH 2 CH 2 , C(CH 3 ) 2 , SiMe 2 , SiPh 2 , SiMePh, silylcyclobutyl (Si(CH 2 ) 3 , (Ph) 2 C, (p-(Et) 3 SiPh) 2 C and silylcyclopentyl (Si(CH 2 ) 4 ).
  • 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 dichlonde or difluoride) or a bisphenoxide, particularly for use with an alumoxane activator.
  • a dihalide such as dichlonde or difluoride
  • a bisphenoxide particularly for use with an alumoxane activator.
  • the metallocene may be represented by Formula V, below. FORMULA V;
  • M is hafnium or zirconium, preferably hafnium
  • each X is, independently, selected from the group consisting of a substituted or unsubstituted 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 each X is independently selected from halides and to C hydrocarbyl groups, preferably each X is methyl, ethyl, propyl, butyl, phenyl, benzyl, chloride, bromide, or iodide;
  • each R 8 is, independently, a substituted or unsubstituted C to (3 ⁇ 4 alkyl group; preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or isomers thereof; preferably methyl, n-propyl, or n-butyl; or preferably methyl;
  • each R 9 is, independently, a substituted or unsubstituted C to (3 ⁇ 4 alkyl group; preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or isomers thereof; preferably methyl, n-propyl, or butyl; or preferably n-propyl;
  • each R 10 is hydrogen
  • each R 1 1 , R 12 , and R 13 is, independently, hydrogen or a substituted or unsubstituted hydrocarbyl group, a heteroatom or heteroatom containing group; preferably each R 1 1 , R 12 , and R 13 , is hydrogen;
  • T is a bridging group represented by the formula R 2 a J where J is C, Si or Ge, preferably Si; each R a is, independently, hydrogen, halogen or a to C20 hydrocarbyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl, benzyl, substituted phenyl, and two R a can form a cyclic structure including aromatic, partially saturated or saturated cyclic or fused ring system; further provided that 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.
  • T may also be a bridging group as defined above for R2 a T; and
  • any of adjacent R 1 1 , R 12 , and R 13 groups may form a fused ring or multicenter fused ring system where the rings may be aromatic, partially saturated or saturated.
  • Metallocene 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 dichlonde or difluoride) or a bisphenoxide, particularly for use with an alumoxane activator.
  • a dihalide such as dichlonde or difluoride
  • a bisphenoxide particularly for use with an alumoxane activator.
  • the metallocene compound is rac-dimethylsilyl bis(2- methyl,3-propylindenyl)hafniumdimethyl (V-I), rac-dimethylsilyl bis (2 -methyl, 3- propylindenyl)zirconiumdimethyl (V-II), represented by the formulae below:
  • the metallocene may be represented by Formula VI, below.
  • each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halogens, dienes, amines, phosphines, ethers, or a combination thereof;
  • each R 15 and R 17 are, independently, a to Cg alkyl group; preferably a Q to Cg linear alkyl group, preferably methyl ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, R 15 may be the same or different as R 17 , and preferably are both methyl; and
  • R 15 and R 17 are methyl groups
  • R 16 is a hydrogen
  • R 18 -R 23 are all hydrogens
  • R 24 -R 28 are all methyl groups
  • each X is a methyl group.
  • Catalyst compounds that are particularly useful in this invention include (CpMe 5 )(l,3-Me 2 benz[e]indenyl)HfMe2, (CpMe 5 )(l -methyl-3 -n- propylbenz[e]indenyl)HfMe2, (CpMe5)(l-n-propyl,3-methylbenz[e]indenyl)HfMe2, (CpMe 5 )( 1 -methyl-3 -n-butylbenz[e]indenyl)HfMe 2 , (CpMe 5 )( 1 -n-butyl,3 - methylbenz[e]indenyl)HfMe 2 , (CpMe 5 )(l-ethyl,3-methylbenz[e]indenyl)HfMe2, (CpMe 5 )(l- methyl, 3-ethylbenz[e]indenyl)HfMe2,
  • the "dimethyl" (Me2) after the transition metal in the list of catalyst compounds above is replaced with a dihalide (such as dichloride or difluoride) or a bisphenoxide, particularly for use with an alumoxane activator.
  • a dihalide such as dichloride or difluoride
  • a bisphenoxide particularly for use with an alumoxane activator.
  • 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 alumoxanes, aluminum alkyls, ionizing activators, which may be neutral or ionic, and conventional-type cocatalysts.
  • Preferred activators typically include alumoxane compounds, modified alumoxane compounds, and 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 activators are utilized as an activator in the catalyst composition.
  • Alumoxanes are generally oligomeric compounds containing -Al(Ri)- O- sub-units, where R 1 is an alkyl group.
  • Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane.
  • Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, particularly when the abstractable ligand is an alkyl, halide, alkoxide or amide.
  • alumoxanes Mixtures of different alumoxanes and modified alumoxanes may also be used. It may be preferable to use a visually clear methylalumoxane.
  • a cloudy or gelled alumoxane can be filtered to produce a clear solution or clear alumoxane can be decanted from the cloudy solution.
  • Another alumoxane is a modified methyl alumoxane (MMAO) cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A, covered under patent number U.S. Patent No. 5,041,584).
  • MMAO modified methyl alumoxane
  • the activator is an alumoxane (modified or unmodified)
  • some embodiments select the maximum amount of activator at a 5000-fold molar excess Al/M over the catalyst precursor (per metal catalytic site).
  • the minimum activator-to-catalyst-precursor is a 1 : 1 molar ratio. Alternate preferred ranges include up to 500: 1, alternately up to 200: 1, alternately up to 100: 1, or alternately from 1 : 1 to 50: 1.
  • 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 VT-HO copolymers is bulky as defined herein and is discrete.
  • Aluminum alkyl or organoaluminum compounds which may be utilized as co- activators (or scavengers) include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and the like.
  • 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.
  • Preferred activators are the ionic activators.
  • Examples of neutral stoichiometric activators include tri-substituted boron, tellurium, aluminum, gallium and indium or mixtures thereof.
  • the three substituent groups are each independently selected from alkyls, alkenyls, halogens, substituted alkyls, aryls, arylhalides, alkoxy, and halides.
  • the three groups are independently selected from halogen, mono or multicyclic (including halosubstituted) aryls, alkyls, 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 European publications EP 0 570 982 A; EP 0 520 732 A; EP 0 495 375 A; EP 0 500 944 B l; EP 0 277 003 A; EP 0 277 004 A; U.S. Patent Nos. 5, 153, 157; 5, 198,401 ; 5,066,741; 5,206, 197; 5,241,025; 5,384,299; 5,502, 124; and U.S. Patent Application Serial No. 08/285,380, filed August 3, 1994; all of which are herein fully incorporated by reference.
  • Ionic catalysts can be preparedly reacting a transition metal compound with some neutral Lewis acids, such as Bf ⁇ F ⁇ , which upon reaction with the hydrolyzable 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, N,N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine, triphenylphosphine, and diphenylphosphine, oxoniums from ethers such as dimethyl ether diethyl ether, tetrahydrofuran and diox
  • 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.
  • 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,
  • triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate triphenylphosphonium tetrakis-(2,3 ,4,6-tetrafluorophenyl)borate, triethylsilylium tetrakis-(2,3 ,4,6- tetrafluorophenyl)borate, benzene(diazonium) tetrakis-(2,3,4,6-tetrafluorophenyl)borate, trimethylammonium tetrakis(perfluoronaphthyl)borate, triethylammonium
  • 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 European publications 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 liability to permit displacement by an ethylenically or acetylenically unsaturated monomer during polymerization.
  • scavengers are used such as tri-isobutyl aluminum or tri-octyl aluminum.
  • 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 European publications 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 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 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 a neutral Lewis base
  • (L-H) + is a Bronsted acid
  • 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.
  • activators have been described in U.S. Patent Nos. 5, 153, 157; 5,453,410; European publication EP 0 573 120 B l; PCT publications WO 94/07928; and WO 95/14044. These documents all discuss the use of an alumoxane in combination with an ionizing activator.
  • 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.
  • Other inorganic oxides that may be employed either alone or in combination with the silica, or alumina are magnesia, titania, zirconia, and the like.
  • Other 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. Also, 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 is 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°C to about 70°C, preferably to about 25°C 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 B 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.
  • this invention relates to:
  • the higher olefin copolymer has at least 40% allyl chain ends, at least 50% allyl chain ends, at least 60% allyl chain ends, at least 70% allyl chain ends, or at least 80% allyl chain ends, at least 90% allyl chain ends, at least 95% allyl chain ends;
  • a catalyst system comprising an activator and at least one metallocene compound represented by at least one of the formulae:
  • M is hafnium or zirconium
  • each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halogens, dienes, amines, phosphines, ethers, and a combination thereof, (two X's may form a part of a fused ring or a ring system);
  • each Q is, independently carbon or a heteroatom
  • each R 1 is, independently, a to Cg alkyl group, R 1 may the same or different as R 2 ;
  • each R 2 is, independently, a Ci to Cg alkyl group
  • each R 3 is, independently, hydrogen, or a substituted or unsubstituted hydrocarbyl group having from 1 to 8 carbon atoms, provided however that at least three R 3 groups are not hydrogen;
  • each R 4 is, independently, hydrogen or a substituted or unsubstituted hydrocarbyl group, a heteroatom or heteroatom containing group;
  • R 5 is hydrogen or a C to Cg alkyl group
  • R 6 is hydrogen or a C to Cg alkyl group
  • each R 7 is, independently, hydrogen or a to Cg alkyl group, provided however that at least seven R 7 groups are not hydrogen;
  • R2 a T is a bridging group, where T is a group 14 element (preferably C, Si, or Ge);
  • each R a is, independently, hydrogen, halogen or a to C20 hydrocarbyl
  • R a can form a cyclic structure including aromatic, partially saturated, or saturated cyclic or fused ring system; and further provided that 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; or (v)
  • M is hafnium or zirconium
  • 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 8 is, independently, a Ci to (3 ⁇ 4 alkyl group
  • each R 9 is, independently, a to alkyl group
  • each R 10 is hydrogen
  • each R 1 1 , R 12 , and R 13 is, independently, hydrogen or a substituted or unsubstituted hydrocarbyl group, a heteroatom or heteroatom containing group;
  • T is a bridging group, preferably represented by the formula 2 a J, where J is a group 14 element (preferably C, Si, or Ge);
  • each R a is, independently, hydrogen, halogen or a to C20 hydrocarbyl
  • R a can form a cyclic structure including aromatic, partially saturated or saturated cyclic or fused ring system; and further provided that 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
  • any of adjacent R 1 1 , R 12 , and R 13 groups may form a fused ring or multicenter fused ring system where the rings may be aromatic, partially saturated or saturated; or (vi)
  • M is hafnium or zirconium
  • each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halogens, dienes, amines, phosphines, ethers, or a combination thereof;
  • each R 15 and R 17 are, independently, a C to Cg alkyl group
  • each Rl6, Rl8, R 19 ; R 20 ; R 21 ; R 22 ; R 23 ; R 24 ; R 25 ; R 26 ; R 27 ; and R 28 arQ> independently, hydrogen or a substituted or unsubstituted hydrocarbyl group having from 1 to 8 carbon atoms, wherein the C5 to C40 higher olefin is selected from butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof.
  • a catalyst system comprising an activator and at least one metallocene compound represented by at least one of the formulae: (i) or (ii)
  • M is hafnium or zirconium; each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halogens, dienes, amines, phosphines, ethers, and a combination thereof, (two X's may form a part of a fused ring or a ring system);
  • each Q is, independently carbon or a heteroatom
  • each R 1 is, independently, a to Cg alkyl group, R 1 may the same or different as R 2 ;
  • each R 2 is, independently, a to Cg alkyl group
  • each R 3 is, independently, hydrogen or a substituted or unsubstituted hydrocarbyl group having from 1 to 8 carbon atoms, provided however that at least three R 3 groups are not hydrogen;
  • each R 4 is, independently, hydrogen or a substituted or unsubstituted hydrocarbyl group, a heteroatom or heteroatom containing group;
  • R 5 is hydrogen or a C to Cg alkyl group
  • R 6 is hydrogen or a Q to Cg alkyl group
  • each R 7 is, independently, hydrogen or a to Cg alkyl group, provided however that at least seven R 7 groups are not hydrogen;
  • R2 a T is a bridging group, where T is a group 14 atom, preferably C, Si, or Ge;
  • each R a is, independently, hydrogen, halogen or a to C20 hydrocarbyl
  • R a can form a cyclic structure including aromatic, partially saturated or saturated cyclic or fused ring system; and further provided that 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;
  • M is hafnium or zirconium
  • 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 8 is, independently, a to alkyl group
  • each R 9 is, independently, a to alkyl group
  • each R 10 is hydrogen
  • each R 1 1 , R 12 , and R 13 is, independently, hydrogen or a substituted or unsubstituted hydrocarbyl group, a heteroatom or heteroatom containing group;
  • T is a bridging group, preferably represented by the formula R2 a J, where J is a group 14 element (preferably C, Si, or Ge);
  • each R a is, independently, hydrogen, halogen or a to C20 hydrocarbyl
  • R a can form a cyclic structure including aromatic, partially saturated, or saturated cyclic or fused ring system; and further provided that 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 11 , R 12 , and R 13 groups may form a fused ring or multicenter fused ring system where the rings may be aromatic, partially saturated or saturated;
  • each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halogens, dienes, amines, phosphines, ethers, or a combination thereof;
  • each R 15 and R 17 are, independently, a Q to Cg alkyl group
  • each R16, Rl8 ; R 19 ; R 20 ; R 21 ; R 22 ; R 23 ; R 24 ; R 25 ; R 26 ; R 27 ; and R 28 arej independently, hydrogen or a substituted or unsubstituted hydrocarbyl group having from 1 to 8 carbon atoms.
  • 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 a fluoride or a perfluorinated aromatic hydrocarbyl 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 Q to C20 hydrocarbyl or hydrocarbylsilyl group, preferably a fluoride or a perfluorinated aromatic hydrocarbyl group;
  • L is a neutral Lewis base
  • H is hydrogen
  • 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) te
  • a composition comprising the higher olefin copolymers of paragraphs 1 to 5 or made by the process of paragraphs 6 to 9, preferably the composition is a lubricant blend.
  • composition of paragraph 10 as a lubricant.
  • Mn, Mw, and Mz were measured by using a High Temperature Size Exclusion Chromatograph (SEC, either from Waters Corporation or Polymer Laboratories), equipped with a differential refractive index detector (DRI).
  • SEC High Temperature Size Exclusion Chromatograph
  • DRI differential refractive index detector
  • Solvent for the SEC experiment was 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 was then filtered through a 0.7 ⁇ glass pre-filter and subsequently through a 0.1 ⁇ Teflon filter. The TCB was then degassed with an online degasser before entering the SEC. Polymer solutions were 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 were 1.463 g/mL at room temperature and 1.324 g/mL at 135°C.
  • the injection concentration was from 1.0 to 2.0 mg/mL, with lower concentrations being used for higher molecular weight samples.
  • Prior to running each sample the DRI detector and the injector were purged. Flow rate in the apparatus was then increased to 0.5 mL/minute, and the DRI was allowed to stabilize for 8 to 9 hours before injecting the first sample.
  • the concentration, c, at each point in the chromatogram was calculated from the baseline-subtracted DRI signal, I DR1 , 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 was expressed in g/cm 3
  • molecular weight was expressed in g/mol
  • intrinsic viscosity was expressed in dL/g.
  • NMR data was 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 frequency of 250 MHz, 400 MHz, or 500 MHz (for the purpose of the claims, a proton frequency of 400 mHz was used). Data was recorded using a maximum pulse width of 45°C, 8 seconds between pulses and signal averaging 120 transients. Spectral signals were integrated and the number of unsaturation types per 1000 carbons was calculated by multiplying the different groups by 1000 and dividing the result by the total number of carbons. Mn was calculated by dividing the total number of unsaturated species into 14,000, and has units of g/mol.
  • the chemical shift regions for the olefin types are defined to be between the following spectral regions.
  • Viscosity was measured using a Brookfield Digital Viscometer.
  • Polymerization grade propylene was used and further purified by passing it through a series of columns: 2250 cc Oxyclear cylinder from Labclear (Oakland, CA), followed by a 2250 cc column packed with dried 3A mole sieves purchased from Aldrich Chemical Company (St. Louis, MI), two 500 cc columns packed with dried 5A mole sieves purchased from Aldrich Chemical Company, one 500cc column packed with ALCOA Selexsorb CD (7x14 mesh) purchased from Coastal Chemical Company (Abbeville, LA), and one 500cc column packed with ALCOA Selexsorb COS (7x14 mesh) purchased from Coastal Chemical Company.
  • Triisobutyl aluminum (TIBAL) was obtained from Akzo Chemicals, Inc. (Chicago, IL) and used without further purification.
  • Tri n-octyl aluminum (TNOAL) was obtained from Akzo Chemicals, Inc. and used without further purification.
  • PPR Cell Parallel Pressure Reactors
  • the PPRs were prepared for polymerization by purging with dry nitrogen at 150°C for 5 hours and then at 25°C for 5 hours.
  • Example 1 Decene-Propylene, Hexene-Propylene, and Decene-Hexene-Propylene Polymerizations with Metallocenes E and F
  • the reactor was prepared as described above, and then charged with 1-decene and/or 1-hexene. The reactors were heated to 25°C and propylene was then charged to the reactor. A solution of scavenger/co-catalyst at process temperature and pressure was next added to the reactors via syringe. The reactors were heated to process temperature (85°C) and stirred at 800 RPM.
  • Metallocene catalysts were mixed with the activator and stirred in toluene at ambient temperature and pressure and added to the reactors (at process temperature and pressure) via syringe as a solution to initiate polymerization. Because the solutions are added via syringe, a hexanes solution is also injected via the same syringe following their addition to insure that minimal solution is remaining in the syringe. This procedure is applied after the addition of the scavenger/co-catalyst solution as well as the catalyst solution.
  • Runs Al, A2, and A5 are copolymerizations of propylene and hexene, using metallocene E and activator III.
  • Runs El and E4 are copolymerizations of propylene and hexene, using metallocene F and activator II.
  • the inventors observed that with increasing propylene content there was a concurrent increase in % vinyls. Also, with decreasing propylene feed, there was an observed increase in Mn, presumably through incorporation of more of the higher molecular weight hexene.
  • Runs B l, B3, and B6 are terpolymerizations of propylene, hexene, and decene, using metallocene E and activator III.
  • Runs F 1 and F3 are terpolymerizations of propylene, hexene, and decene, using metallocene F and activator II. It was similarly observed that with increasing propylene content, there was a concurrent increase in % vinyls. Also, with decreasing propylene feed, there was an observed increase in Mn, presumably through incorporation of more of the higher molecular weight hexene and decene.
  • Solution runs were performed as follows: propylene was first added to the reaction cell, then octene and isohexane was added such that the total solution volume was 5.0 mL. TNOAL was used as scavenger at a concentration of 1 M. A solution of activator III in toluene was added first followed by a solution of the metallocene E or F such that the activator to metallocene ratio was 1 : 1. The cells were heated to 85°C and the reaction proceeded for 1 hour. The reaction was quenched with air and unreacted monomers were removed in vacuo. Analysis of some of the cell products are listed in Table 2B.
  • VYD vinylidene
  • Example 4 Decene-Propylene Polymerization (Comparison of Metallocene E with Comparative Metallocenes A, B. & C
  • Anhydrous toluene was purchased from Sigma Aldrich (Chicago, IL) and was further dried over 4 A molecular sieves under an inert atmosphere.
  • the catalyst charger containing the metallocene/activator solution was attached to the reactor at an entry port.
  • a high pressure nitrogen line was attached to the charger to discharge the catalyst into the reactor at the appropriate time.
  • the vent line to the reactor was closed. Using less than one pound of pressure purging out of the reactor, the higher olefin comonomer was syringed into the bottom of the reactor, using a second port. Then, using the same port, the scavenger was charged into the reactor, and the port closed.
  • the nitrogen line to the reactor was closed. Isohexane was added to the reactor, followed by of propylene.
  • the agitator was started at 800 rpm, and the reactor heated to the required process temperature.
  • compositions, an element or a group of elements are preceded with the transitional phrase "comprising,” it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of,” “selected from the group of consisting of,” or “is” preceding the recitation of the composition, element, or elements and vice versa.

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  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

L'invention concerne un copolymère d'oléfines supérieures à terminaison vinyle présentant un Mn supérieur ou égal à 300 g/mol (mesuré par 1H NMR) qui comprend : (i) entre environ 20 et environ 99,9 mol % d'au moins un monomère d'oléfines supérieures C5 à C40 ; et (ii) entre environ 0,1 et environ 80 mol % de propylène ; le copolymère d'oléfines supérieures possédant au moins 40 % d'extrémités de chaîne allyle. Le copolymère peut également présenter un rapport extrémité de chaîne isobutyle/extrémité de chaîne allyle inférieur à 0,7: 1 et/ou un rapport extrémité de chaîne allyle/extrémité de chaîne vinylidène supérieur à 2:1.
PCT/US2012/027682 2011-03-25 2012-03-05 Polymères d'oléfines supérieures à terminaison vinyle et leurs procédés de production Ceased WO2012134717A2 (fr)

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CN201280014747.1A CN103443144B (zh) 2011-03-25 2012-03-05 乙烯基封端的高级烯烃共聚物及其制造方法
EP12763904.5A EP2688926A4 (fr) 2011-03-25 2012-03-05 Polymères d'oléfines supérieures à terminaison vinyle et leurs procédés de production

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US13/072,249 US8399724B2 (en) 2011-03-25 2011-03-25 Vinyl terminated higher olefin copolymers and methods to produce thereof
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US10501642B2 (en) 2014-12-04 2019-12-10 Exxonmobil Chemical Patents Inc. Stable star-structured functional polyolefins

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EP2897726A4 (fr) * 2012-09-24 2016-06-22 Exxonmobil Chem Patents Inc Production de polyéthylène à terminaison vinylique
US10501642B2 (en) 2014-12-04 2019-12-10 Exxonmobil Chemical Patents Inc. Stable star-structured functional polyolefins
US11053396B2 (en) 2014-12-04 2021-07-06 Exxonmobil Chemical Patents Inc. Stable star-structured functional polyolefins

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JP5739054B2 (ja) 2015-06-24
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EP2688926A4 (fr) 2015-07-08
JP2014511910A (ja) 2014-05-19
EP2688926A2 (fr) 2014-01-29

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