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WO2000040625A1 - Copolymeres d'ethylene a repartition etroite de la composition et a temperatures de fusion elevees, et procedes de production desdits copolymeres - Google Patents

Copolymeres d'ethylene a repartition etroite de la composition et a temperatures de fusion elevees, et procedes de production desdits copolymeres Download PDF

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Publication number
WO2000040625A1
WO2000040625A1 PCT/US1999/015518 US9915518W WO0040625A1 WO 2000040625 A1 WO2000040625 A1 WO 2000040625A1 US 9915518 W US9915518 W US 9915518W WO 0040625 A1 WO0040625 A1 WO 0040625A1
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Prior art keywords
copolymer
comonomer
ethylene
copolymers
composition distribution
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PCT/US1999/015518
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English (en)
Inventor
Robert M. Waymouth
Jennifer L. Maciejewski Petoff
Raisa L. Kravchenko
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The Board Of Trustees Of The Leland Stanford Junior University
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Priority claimed from US09/227,228 external-priority patent/US6169151B1/en
Application filed by The Board Of Trustees Of The Leland Stanford Junior University filed Critical The Board Of Trustees Of The Leland Stanford Junior University
Priority to JP2000592333A priority Critical patent/JP2002534538A/ja
Priority to AU49793/99A priority patent/AU4979399A/en
Priority to CA002322496A priority patent/CA2322496A1/fr
Priority to EP99933817A priority patent/EP1062257A1/fr
Publication of WO2000040625A1 publication Critical patent/WO2000040625A1/fr

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    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • 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
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • 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

Definitions

  • thermoplastic polyolefins More particularly, this invention relates to copolymers of ethylene with C 4+ olefin monomers which typically contain blocky structures as shown by peak melting temperatures above those measured in corresponding random copolymers with similar monomer composition, and to methods of production by use of fluxional metallocane catalysts.
  • Thermoplastic olefin polymers represent a significant worldwide market with millions of tons of these polymers produced and sold each year. Copolymers of ethylene with C 4+ monomers are a substantial fraction of the worldwide olefin polymer production, especially in use as films. Although the bulk of ethylene polymers are thermoplastics, there is a growing further need for elastomeric thermoplastic olefin polymers. Copolymers of ethylene with higher (C 4+ ) olefin monomers are well known and used in the art. Among these are linear low density polyethylenes conventionally produced as a copolymer of ethylene with 1-butene or 1-octene using traditional Ziegler-Natta catalyst systems. These materials typically have broad polydispersities, and broad composition distributions
  • ethylene-C 4+ copolymers have a particularly broad range of application as elastomers
  • elastomers There are generally three families of elastomers made from such copolymers
  • One class is typified by ethylene-propylene copolymers (EPR) which are saturated compounds, optimally of low crystallmity, requiring vulcanization with free-radical generators to achieve excellent elastic properties
  • Another class of elastomer is typified by ethylene-propylene terpolymers (EPDM), again optimally of low crystallmity, which contain a small amount of a non- conjugated diene such as ethy dene norbornene
  • EPDM ethylene-propylene terpolymers
  • This invention relates to copolymers of ethylene with C + olefin monomers which may be thermoplastics or elastomers Particularly, these copolymers typically are formed from a fluxional catalyst system which creates properties consistent with a blocky structure
  • a polymer chain with a blocky structure will contain segments of differing compositional microstructure
  • ethylene/hexene copolymer of this invention the evidence indicates ethylene homopolymer blocks are distributed in the polymer chain with adjacent segments of ethylene/hexene copolymer Since ethylene homopolymer segments will form regions of polyethylene crystallmity while ethylene/hexene copolymer segments will be amorphous, the polymer as a whole contains regions of polyethylene crystallmity interspersed with amorphous regions to a greater extent than would be observed in a copolymer of ethylene with randomly dispersed comonomer Typically the upper peak melting temperatures for the copolymers of this invention are higher than corresponding random copolymers, although the
  • the high melting crystals are a result of the non-random comonomer incorporation allowing the formation of longer runs of ethylene homopolymer sequences than occurs in random versions
  • copolymers of the invention show a narrow compositional distribution among fractions separated by crystallmity or molecular weight
  • the copolymers of this invention show improved optical properties, such as clarity and reduced haze in films, as follows from a narrower composition distribution
  • the copolymers of the invention also exhibit a relatively broad polydisperity, a property which results in superior processibility
  • the olefin copolymers of the invention are characterized by low glass transition temperatures, melting points above about 90°C, high molecular weights and a narrow composition distribution between chains
  • the copolymers of the invention are novel reactor blends that can be sequentially fractionated into fractions of differing crystallmities These fractions nevertheless show compositions of comonomers which differ by less than 15% from the parent reactor blend
  • the invention also relates to a process for producing such copolymers by using unb ⁇ dged fluxional metallocene catalysts that are capable of mterconverting between states, each state having different copolyme ⁇ zation characteristics, i e , each state having a different relative rate of insertion of a given ethylene or C 4+ monomer into the growing copolymer chain and preferential selectivity for different monomers under particular reaction conditions
  • copolymers of this invention are produced using a new family of fluxional metallocene-based catalysts first described in U S Patent 5,594,080, incorporated by reference herein These catalysts produce blocky structures in the polymer chain which yield polymer products having a combination of properties which is advantageous for multiple use applications including films This combination of properties include a narrow composition distribution, broad polydispersity, and a broad melting transition with an upper melting peak which typically is higher than a randomly distributed copolymer with the same monomer unit composition
  • Products made from the copolymers of this invention benefit from the products improved processibihtiy of the polymer, higher temperature performance range, and uniformity Applications include films, including heat sealable films, and molded products More particularly with respect to films, films can be produced with improved optical properties such as low haze and improved clarity
  • the copolymers of the Invention can be characterized as copolymers of ethylene and at least one comonomer containing at least 4 carbon atoms having a polydispersity greater than 2, a broad melting point transition as measured by differential scanning calorimetry, and a narrow composition distribution
  • Ethylene/ C + copolymers of the invention also may show at least one peak melting point above the peak melting point of a random copolymer of the same monomer unit composition
  • These copolymers are made by contacting ethylene and a comonomer under polymerization conditions in the presence of a suitable fluxional metallocene catalyst system
  • Fig. 1 is a stereoisome ⁇ c representation of unb ⁇ dged metallocenes used in this invention having different substituents in the positions R-
  • Fig. 2 shows four possible coordination geometries for unbndged metallocenes used in this invention with the circles representing coordination sites for olefin insertion,
  • Fig. 3 shows superimposed DSC thermograms for ethylene-1 -hexene copolymers produced with differing amounts of hydrogen, wherein the trace (a) product had no H2 added, trace (b) product has 2 5 mmol H2 added, and trace (c) product has 5 0 mmol H2 added,
  • Fig. 4 shows a DSC profile for an ethylene-1 -hexene copolymer containing 72 mol % ethylene, wherein the top trace is a standard DSC and the bottom is a SFT trace,
  • Fig. 5 shows melting temperature vs composition plotted for the ethylene-1 - hexene copolymer of Example 19 with its solvent fractions (cf Table 9), and by way of comparison also plotted is data for random alpha-olefm copolymers, and
  • Fig. 6 shows melting temperature vs composition plotted for the ethylene-1 - hexene copolymer of Example 7 with its solvent fractions (cf Table 5), and by way of comparison also plotted is data for random alpha-olefm copolymers
  • the invention is illustrated in the several examples, and is of sufficient complexity that the many aspects, interrelationships, and sub- combinations thereof simply cannot be fully illustrated in a single example
  • several of the examples show, or report only aspects of a particular feature or principle of the invention, while omitting those that are not essential to or illustrative of that aspect
  • the best mode embodiment of one aspect or feature may be shown in one example or test, and the best mode of a different aspect will be called out in one or more other examples, tests, structures, formulas, or discussions
  • Multiblock polymer or copolymer means a polymer comprised of multiple block sequences of monomer units where the structure or composition of a given sequence differs from that of its neighbor Furthermore, a multiblock copolymer as defined herein will contain a given sequence at least twice in every polymer chain
  • composition distribution is the variation in co-monomer composition between different polymer chains and is described as a difference, in mole percent, of a given weight percent of a fractionated sample from the mean mole percent composition
  • the distribution need not be symmetrical around the mean, when expressed as a number (for example 10%), that number represents the larger of the distributions from the mean
  • elastomeric refers to a material which tends to regain its shape after extension, such as one which exhibits a positive power of recovery after 100, 200 and 300% elongation
  • crystallizable component we mean a monomer component whose homopolymer is a crystalline polymer For ethylene copolymers exhibiting polyethylene crystallmity, the crystallizable component is ethylene
  • Tm melting point
  • DSC differential scanning calorimetry
  • Copolymers of this invention are characterized by a broad melting range as exhibited in a DSC thermogram, a narrow composition distribution over fractions separated by crystallmity or molecular weight, and a relatively broad molecular weight distribution (or polydispersity) This combination of characteristics produce an ethylene copolymer product having distinct and commercially significant properties
  • copolymers of this invention are formed from ethylene and an olefin monomer containing from 4 up to about 20 carbon atoms and typically from 4 to about 10 carbon atoms, herein termed a "C + " monomer
  • Preferable comonomers contain from 4 to 8 carbons
  • Representative comonomers include 1-butene, 1- pentene, 1 -hexene, 4-methyl-1-pentene, 1-octene, and 1-decene Butene, hexene, octene monomers are preferred with hexene being the most preferred Mixtures of comonomers may be used
  • the amount of comonomer which is incorporated into the copolymers of this invention may vary depending upon the properties desired Typically, copolymers of this invention contain up to about 50 mole % (preferably up to 40 mole %) of comonomers Typical copolymers may contain up to 30 or up to 10 mole percent of comonomers
  • copolymers of this invention may contain up to 10 and preferably up to 5 mole percent comonomers
  • the minimum amount of comonomer used in this invention depends on the amount of comonomer which is needed to alter the properties of ethylene homopolymer This amount typically is greater than about one mole percent and often is more than about two mole percent
  • the properties of the copolymer produced according to this invention may vary from elastomeric to those of a thermoplastic Copolymers of the invention containing more than about 10 mole percent comonomer content typically have elastomeric properties
  • addition of hydrogen to the polymerization reaction can result in production of a plastomer having the same monomer composition as a copolymer which is an elastomer when hydrogen is not added
  • the ethylene copolymer products of the invention typically exhibit bimodai or multimodal crystalline melting temperature transitions with a broad region of crystalline melting
  • a crystalline melting temperature, T m may be assigned to the highest temperature peak in a DSC thermogram as illustrated in Fig 3
  • a copolymer of this invention typically shows a broad melting temperature region and a low temperature melting point peak
  • a broad melting point range in a DSC thermogram indicates a distribution of crystals of different sizes and thermodynamic stabilities and correspondingly a distribution of crystallizable sequences in the polymer chains Peaks in the thermogram indicate increased concentrations of crystals with similar stabilities
  • there may be separated bimodai melting ranges This indicates that most of the polymer chains have higher concentrations of high and low melting crystals and a lower concentration of crystals that melt at intermediate temperatures
  • Polymers of this invention show a broad melting point range from the minimum to maximum melting temperature of from over 50 °C more than to 150 °C or above.
  • polymers may have melting temperature ranges of above 75 °C (often greater than 100 °C) up to about a 150 °C range.
  • melting temperature ranges of above 75 °C (often greater than 100 °C) up to about a 150 °C range.
  • maxima (reported as T m 's) in the DSC thermograms within these broad ranges.
  • Copolymers of this invention typically have molecular weight distributions (Mw/Mn) or polydispersities above 2 and usually above 3. Useful polydispersities may range up to 12 or above. Preferable copolymers of this invention have polydispersities ranging from about 3 to about 10 and more preferably from about 4 to about 9.
  • the distribution of monomer unit composition is narrow in product fractions that are separated by crystallinity or molecular weight.
  • solvent fractionated products which generally separate polymer chains by crystallinities
  • the range of co-monomer composition distribution typically varies by less than about 15 mole percent (15 mole %), preferably varies by less than about 12 mole %, and more preferably varies by less than 8-10 mole %. Even though the composition distribution is narrow for these fractions, the melting transitions measured by DSC may vary substantially among the solvent fractions.
  • the solvents used for fractionation include diethylether (ether), hexanes (saturated C 6 isomers), and n-heptane at reflux conditions. Other compatible solvents may be used.
  • the polymers of this invention also typically exhibit very narrow composition distribution within fractions separated by molecular weight through a supercritical propane fractionation procedure.
  • solubility of a polymer in a fluid, such as propane, at supercritical conditions is a function of pressure.
  • supercritical fluid fractionation may be used to separate fractions of linear low density polyethylenes according to molecular weight and degree of short chain branching.
  • copolymers of the present invention in one preferred embodiment can be characterized as reactor blends in that they can be fractionated into fractions of differing degrees of crystallinity and differing melting points. Nevertheless, the comonomer composition of the various fractions of the copolymers are all within 15% of the composition of the resultant polymer product produced in the reactor.
  • the melting points of the copolymers of the present invention are high, typically above 90 °C and the melting point indices, T m / X c are also high, typically above 80 °C and preferably above 115°C.
  • the individual fractions can also exhibit high melting point indices. For example, it is possible to isolate a hexanes soluble fraction from the copolymers of the present invention that exhibits a melting point as high as 115 °C and a melting point index as high as 160 °C.
  • the glass transition temperatures (Tg) of the copolymers are low, typically less than -20 °C and preferably below -50 °C.
  • the molecular weight of the polymer product can be controlled, optionally, by controlling the temperature or by adding any number of chain transfer agents such as hydrogen or metal alkyls, as is well known in the art. While not wishing to be bound by theory, it is believed that in the process of the invention, different active species of the fluxional catalyst are in equilibrium during the construction of the copolymer chains.
  • a class of unbridged metallocenes that are capable of isomerizing between states that have different copolymerization characteristics during the polymerization process, i.e. each state having a different relative rate of insertion of a given ethylene or C 4+ monomer into the growing copolymer chain and preferential selectivity for different monomers under particular reaction conditions.
  • the process of the invention thus leads to muitiblock copolymers or copolymer blends wherein the blocks or components of the blends have different compositions of comonomers.
  • the catalysts used in the present invention comprise unb dged, non-rigid (fluxional) metallocenes which can change their geometry with a rate that is within several orders of magnitude of the rate of formation of a single polymer chain, on average.
  • the relative rates of interconversion and of formation can be controlled by selecting the substituents (or absence thereof) on the cyclopentadienyl ligands so that they can alternate in structure between states of different coordination geometries which have different selectivity toward a particular comonomer.
  • One embodiment of the invention includes metallocene catalysts which are able to interconvert between states whose coordination geometries are different.
  • the invention includes selecting the substituents of the metallocene cyclopentadienyl ligands so that the rate of interconversion of the two states is within several orders of magnitude of the rate of formation of a single polymer chain. That is, if the rate of interconversion between states of the catalyst, ⁇ , is greater than the rate of formation of an individual polymer chain, rf , on average, the polymer resulting from use of the inventive process and catalysts can be characterized as multiblock (as defined above). If the rate of interconversion is less than the rate of formation, the result is a polymer blend. Where the rates are substantially balanced, the polymer can be characterized as a mixture of blend and multiblock. There may be a wide range of variations and intermediate cases amongst these three exemplars.
  • the nature of the substituents on the cyclopentadienyl ligands is critical; the substitution pattern of the cyclopentadienyl ligands should be such that the coordination geometries are different in order to provide different reactivities toward ethylene and other alpha olefins while in the two (or more) states (see Figure 1 ), and that the rate of interconversion of the states of the catalyst are within several orders of magnitude of the rate of formation of a single chain. While not wishing to be bound by theory, it is currently believed that sterically demanding cyclopentadienyl substitients, such as a 3,5-disubstituted aryl group, provide optimized rates of interconversion between the two states.
  • a further embodiment includes metallocene catalysts which are able to mterconvert between more than two states whose coordination geometries are different This is provided for by metallocenes with cyclopentadienyl-type ligands substituted in such a way that more than two stable states of the catalyst have coordination geometries that are different For example, one embodiment of a catalyst with four geometries is illustrated in Figure 2
  • the properties of the copolymers can be controlled by changing one or more of the nature of the cyclopentadienyl units on the catalysts, the nature of the metal atom in the catalyst, and by changing the process conditions e g , by changing the nature of the comonomers, the comonomer feed ratio, the temperature, by presence of hydrogen, and/or control of other conventional process conditions
  • Catalyst systems useful to produce copolymer of the present invention typically contain a transition metal component metallocene in the presence of an appropriate cocatalyst
  • the transition metal compounds have the formula
  • M is a Group 3, 4 or 5 Transition metal, a Lanthanide or an Actmide
  • X and X' are the same or different unmegative ligands, such as but not limited to hydride, halogen, hydrocarbyl, halohydrocarbyl, amine, amide, or borohydnde substituents (preferably halogen, alkoxide, or Ci to C7 hydrocarbyl)
  • L and L' are the same or different polynuclear hydrocarbyl, silahydrocarbyl, phosphahydrocarbyl, azahydrocarbyl, arseni-hydrocarbyl or borahydrocarbyl rings, typically a substituted cyclopentadienyl ring or heterocyclopentadienyl ring, in combination with an appropriate cocatalyst
  • Exemplary preferred Transition Metals include titanium, vanadium, and, more preferably, zirconium or hafnium
  • L and L' have the formula
  • , R2, R3, R9 and R10 may be the same or different hydrogen, alkyl, alkylsiiyl, aryl, alkoxyalkyl, alkoxyaryl, alkoxysilyl, aminoalkyl, aminoaryl or substituted alkyl. alkylsiiyl or aryl substituents of 1 to about 30 carbon atoms.
  • Ligands of this general structure include substituted cyclopentadienes.
  • Other ligands L and L' of Formula 2 for the production of ethylene copolymers include substituted cyclopentadienes of the general formula:
  • R2-R10 have the same definition as R1 , R2, R3, Rg, and R-J O above.
  • L and L' of Formula 1 include ligands of Formula 2 wherein R is an aryl group, such as a substituted phenyl, biphenyl, or naphthyl group, and R2 and R3 are connected as part of a ring of three or more carbon atoms.
  • R is an aryl group, such as a substituted phenyl, biphenyl, or naphthyl group
  • R2 and R3 are connected as part of a ring of three or more carbon atoms.
  • L or L' of Formulas 1- 3 for producing the copolymers of this invention are substituted indenyl ligands, more particularly 2-arylindene of formula:
  • R4 - R14 may be the same or different hydrogen, halogen, aryl, hydrocarbyl, silahydrocarbyl, or halohydrocarbyl substituents. That is, R-
  • Preferred 2-aryl indenes include ligands in which R5 and R7 are substituents other than hydrogen such as aryl, hydrocarbyl, silahydrocarbyl, alkylsiiyl, or halohydrocarbyl containing up to about 12 carbon atoms.
  • substituents include Ci-C ⁇ alkyls (preferably C ⁇ -C ⁇ branched alkyls such as isopropyl, isobutyl, s-butyl, t-butyl, isoamyl), halogenated alkyls, and alkylsilyls, Particularly preferred sustituents are bulky such as t-butyl, triflouromethyl, and trimethylsilyl.
  • ligands contain a non-hydrogen Rg or R-
  • Preferred substituents include lower (C-
  • a system containing an Rg or R ⁇ Q substituent will create a fluxional metallocene catalyst system containing more than two rotational symmetry states.
  • the fluxional catalyst system contains a metallocene component containing two different ligands having preselected substituents that provide the requisite mterconverting states as described above
  • 2-Aryl indenes useful to make fluxional metallocene catalysts in this invention include
  • 2-(3,5-b ⁇ s-tertbutylphenyl) indene 1-methyl-2-(3,5-b ⁇ s-tertbutylphenyl) indene, 2-(3,5-b ⁇ s-t ⁇ methyl- s ⁇ lylphenyl) ⁇ ndene, 1 -methyl-2-(3 5-b ⁇ s-t ⁇ methyls ⁇ lylphenyl) ⁇ ndene, 2-(4-fluorophenyl) indene, 2-(2, 3, 4, 5-tetrafluorophenyl) indene,
  • Typical fluxional metallocenes useful in this invention include b ⁇ s[2-(3,5-d ⁇ methylphenyl) ⁇ ndenyl] zirconium dichlo ⁇ de, b ⁇ s[2-(3,5-b ⁇ s-tr ⁇ fluoromethylphenyl) ⁇ ndenyl] zirconium dichlo ⁇ de, b ⁇ s[2-(3,5-b ⁇ s-tertbutylphenyl) ⁇ ndenyl] zirconium dichlo ⁇ de, b ⁇ s[2-(3,5-b ⁇ s-t ⁇ methyls ⁇ lylphenyl) ⁇ ndenyl] zirconium dichlo ⁇ de, b ⁇ s[2-(4,-fluorophenyl) ⁇ ndenyl] zirconium dichlo ⁇ de, b ⁇ s[2-(2,3,4,5,-tetrafluorophenyl) ⁇ ndenyl] zirconium dichlo ⁇ de, b ⁇ s(2-(2,3,4,5,6-penta
  • Typical fluxional metallocenes useful in this invention also include the corresponding hafnium compounds such as: bis[2-(3,5-dimethylphenyl)indenyl] hafnium dichloride; bis[2-(3,5-bis-trifiuoromethyphenyl)indenyl] hafnium dichloride; bis[2-(3,5-bis-tertbutylphenyl)indenyl] hafnium dichloride; bis[2-(3,5-bis-trimethylsilylphenyl) indenyl] hafnium dichloride; bis[2,(4-fluorophenyl)indenyl] hafnium dichloride; bis[2-(2,3,4,5-tetrafluorophenyl)indenyl] hafnium dichloride; bis[2-(2,3,4,5,6-pentafluorophenyl)indenyl] hafnium dichloride; bis[2-(1-naphthyl)in
  • Particularly preferred metallocene components include b ⁇ s[2-(3,5-b ⁇ s-t ⁇ fluoromethyphenyl) ⁇ ndenyl] hafnium dichloride, b ⁇ s[2-(3,5-b ⁇ s-tertbutylphenyl) ⁇ ndenyl] hafnium dichloride, b ⁇ s[2-(3,5-b ⁇ s-t ⁇ methyls ⁇ lylphenyl) mdenyl] hafnium dichloride, [1-methyl-2-(3,5-b ⁇ s-t ⁇ fluoromethylphenyl) ⁇ ndenyl](2-phenyl ⁇ ndenyl) zirconium dichloride, [1-methyl-2-(3,5-b ⁇ s-t ⁇ fluoromethylphenyl) ⁇ ndenyl][2-(3,5-b ⁇ s- t ⁇ fluoromethylphenyl) ⁇ ndenyl] zirconium dichloride, b ⁇ s[2-(3,5-b ⁇ s-t ⁇
  • metallocenes are prepared by forming the mdenyl ligand followed by metallation with the metal tetraha de to form the complex in synthetic procedures known to the art
  • cocatalysts include alkylaluminum compounds, methylaluminoxane, or modified methylalummoxanes, as illustrated in U S Patent 4,542,199 to Kammsky, et al , Ewen, J Am Chem Soc , 106 (1984), p 6355, Ewen, et al , J Am Chem Soc 109 (1987) p 6544 Ewen, et al , J Am Chem Soc 110 (1988), p 6255, Kammsky, et al, Angew Chem , Int Ed Eng 24 (1985), p 507
  • Other useful cocatalysts include Lewis or protic acids, such as B(C6Fs)3 or (PhNMe2H) B(C6F5)4 ⁇ , which generate cationic metallocenes with compatible non-coordinating anions in the presence or absence of alkyl-aluminum compounds Catalyst systems employing a cationic Group 4
  • these catalyst systems may be placed on a suitable support such as silica, alumina, or other metal oxides, magnesium halide such as MgCl2 or other supports.
  • a suitable support such as silica, alumina, or other metal oxides, magnesium halide such as MgCl2 or other supports.
  • These catalysts can be used in the solution phase, in slurry phase, in the gas phase, or in bulk monomer. Both batch and continuous polymerizations can be carried out.
  • solvents for solution polymerization include liquefied monomer, and aliphatic or aromatic solvents such as toluene, benzene, hexane, heptane, diethyl ether, as well as halogenated aliphatic or aromatic solvents such as methylene chloride, chlorobenzene, fluorobenzene, hexaflourobenzene or other suitable solvents.
  • aliphatic or aromatic solvents such as toluene, benzene, hexane, heptane, diethyl ether
  • halogenated aliphatic or aromatic solvents such as methylene chloride, chlorobenzene, fluorobenzene, hexaflourobenzene or other suitable solvents.
  • Use of liquid hydrocarbon is preferred, such as hexane or heptane, to avoid halogenated waste streams.
  • Various agents can be added to control the molecular weight, including hydrogen,
  • the copolymers of this invention are prepared by contacting ethylene and at least one co-monomer with the above-described catalyst system under suitable polymerization conditions.
  • suitable polymerization conditions include polymerization or copolymerization temperature and time, pressure(s) of the monomer(s), avoidance of contamination of catalyst, choice of polymerization or copolymerization medium in slurry processes, the use of additives to control homopolymer or copolymer molecular weights, and other conditions well known to persons skilled in the art.
  • catalyst or catalyst component is used for the reactor system and process conditions selected.
  • the amount of catalyst will depend upon the activity of the specific catalyst chosen.
  • polymerization or copolymerization should be carried out at temperatures sufficiently high to ensure reasonable polymerization or copolymerization rates and avoid unduly long reactor residence times, but not so high as to cause catalyst deactivation or polymer degradation.
  • temperatures range from about 0°C to about 120°C with a range of from about 20°C to about 95°C being preferred from the standpoint of attaining good catalyst performance and high production rates.
  • a preferable polymerization range according to this invention is about 50°C to about 80°C.
  • Olefin polymerization or copolymerization according to this invention is carried out at monomer pressures of about atmospheric or above. Generally, monomer pressures range from about 20 to about 600 psi (140 to 4100 kPa), although in vapor phase polymerizations or copolyme ⁇ zations, monomer pressures should not be below the vapor pressure at the polymerization or copolymerization temperature of the alpha-olefin to be polymerized or copolyme ⁇ zed
  • the polymerization or copolymerization time will generally range from about 1/2 to several hours in batch processes with corresponding average residence times in continuous processes Polymerization or copolymerization times ranging from about 1 to about 4 hours are typical in autoclave-type reactions In slurry processes, the polymerization or copolymerization time can be regulated as desired Polymerization or copolymerization times ranging from about 1/2 to several hours are generally sufficient in continuous slurry processes
  • gas-phase polymerization or copolymerization processes in which the catalyst or catalyst component of this invention is useful include both stirred bed reactors and fluidized bed reactor systems and are described in U S Patents 3,957,448, 3,965,083, 3,971 ,786, 3,970,611 , 4,129,701 , 4,101 ,289, 3,652,527, and 4,003,712, all incorporated by reference herein
  • Typical gas-phase olefin polymerization or copolymerization reactor systems comprise at least one reactor vessel to which olefin monomer and catalyst components can be added and which contain an agitated bed of forming polymer particles
  • catalyst components are added together or separately through one or more valve-controlled ports in the single or first reactor vessel
  • Olefin monomer typically, is provided to the reactor through a recycle gas system in which unreacted monomer removed as off-gas and fresh feed monomer are mixed and injected into the reactor vessel
  • a quench liquid which can be liquid monomer, can be added to polymerizing
  • polymerization or copolymerization is carried out under conditions that exclude oxygen, water and other materials that act as catalyst poisons
  • polymerization or copolymerization can be carried out in the presence of additives to control polymer or copolymer molecular weights Hydrogen typically is employed for this purpose in a manner well known to persons of skill in the art
  • Hydrogen typically is employed for this purpose in a manner well known to persons of skill in the art
  • the catalyst upon completion of polymerization or copolymerization, or when it is desired to moderate or terminate polymerization or copolymerization or at least temporarily deactivate the catalyst or catalyst component of this invention, the catalyst can be contacted with water, alcohols, carbon dioxide, oxygen, acetone, or other suitable catalyst deactivators in a manner known to persons of skill in the art
  • the polymerization of olefins according to this invention is carried out by contacting the olefin(s) with the catalyst systems comprising the transition metal fluxional component and in the presence of an appropriate cocatalyst, such as an aluminoxane, a Lewis acid such as B(C6F5)3, or a protic acid in the presence of a non-coordinating counterion such as B(C6Fs)4 ⁇ .
  • an appropriate cocatalyst such as an aluminoxane, a Lewis acid such as B(C6F5)3, or a protic acid in the presence of a non-coordinating counterion such as B(C6Fs)4 ⁇ .
  • the metallocene catalyst systems of the present invention are particularly useful for the polymerization of ethylene and C4+ alpha-olefm co-monomers as well as alpha-olefm monomer mixtures to produce co-polymers with novel thermoplastic, plastomeric and elastomeric properties.
  • the properties of elastomers are characterized by several variables.
  • the tensile set (TS) is the elongation remaining in a polymer sample after it is stretched to an arbitrary elongation (e.g. 100% or 300%) and allowed to recover. Lower set indicates higher elongational recovery.
  • Stress relaxation is measured as the decrease in stress (or force) during a time period (e.g. 30 sec. or 5 min.) that the specimen is held at extension.
  • retained force is measured as the ratio of stress at 50% elongation during the second cycle recovery to the initial stress at 100% elongation during the same cycle. Higher values of retained force and lower values of stress relaxation indicate stronger recovery force. Better general elastomeric recovery properties are indicated by low set, high retained force and low stress relaxation.
  • fluxional metallocene catalysts incorporating hafnium may exhibit increased reactivity to the higher olefin copolymer (such as hexene, r H ) relative to the polymerization reactivity to ethylene (r E ).
  • FIG. 2 Another embodiment of the invention is illustrated in Figure 2 where the ligands L and L' are different substituted 2-arylindenyl ligands such that the metallocene interconverts between four states with different coordination geometries.
  • a methyl group projects over the coordination sites for olefin insertion (represented in this figure by circles) and in two states the methyl group projects away from the coordination sites for the olefin.
  • the following Examples and Comparative Runs illustrate, but do not limit the inventions described herein.
  • Hexane, pentane and methylene chloride used in organometallic synthesis were distilled from calcium hydride under nitrogen. Tetrahydrofuran was distilled from sodium/benzophenone under nitrogen. Toluene, ethylene and propylene were passed through two purification columns packed with activated alumina and supported copper catalyst. 1 -Hexene and chloroform- 3 were distilled from calcium hydride and benzene-d6 was distilled from sodium/benzophenone.
  • Ethylene-bis(indenyl)zirconium dichloride (Metallocene 1): This complex was prepared as described in Wild, F. R. W. P.; Wasiucionek, M.; Huttner, G.; Brintzinger, H. H. J. Organomet. Chem. 1985, 288, 63-7.
  • Bis(2-phenylindenyl)zirconium dichloride (Metallocene 2): This complex was prepared as described in Bruce, M. D.; Coates, G. W.; Hauptman, E.; Waymouth, R. M.; Ziller, j. W. J. Am. Chem. Soc. 1997, 119, 11174-11182.
  • Bis(2-phenylindenyl)hafnium dichloride (Metallocene 3): This complex was prepared as described in Bruce, M. D.; Coates, G. W.; Hauptman, E.; Waymouth, R. M.; Ziller, j. W. J. Am. Chem. Soc. 1997, 119, 11174-11182.
  • Ligand A 2-(Bis-3,5-trifluoromethylphenyl)indene
  • this alcohol (21.5 g, 0.06 mol) and p-toluene-sulfonic acid monohydrate (800 mg) were dissolved in toluene (250 mL) and the solution was heated to reflux for 6 hours to afford 14.4 g, (70%) of 2-(bis-3,5(trifluoromethyl)- phenyl) indene upon recrystallization from diethyl ether/hexane at -18 °C.
  • Metallocene 4 Bis(2-(3,5-trifluoromethylphenyl)indenyl) zirconium dichloride
  • Metallocene 5 Bis(2-(3,5-trifluoromethyiphenyl)indenyl) hafnium dichloride
  • N-Butyllithium (1.6M in hexanes, 2 mL. 3.20 mmol) was added dropwise at room temperature to a solution of 2-(bis-3,5-trifluoromethylphenyl)indene (1.03 g. 3.14 mmol) in diethyl ether (10 mL). After stirring for 30 min, the solvent was removed in vacuo leaving a green-yellow solid. In a drybox, HfCl4, (510 mg, 1.59 mmol) was added to the lithium salt. The solids were then cooled to -78 °C at which temperature toluene (45 mL) was slowly added.
  • the flask was allowed to reach ambient temperature and the suspension was stirred for 24 hours after which time it was heated for 15 min to ca. 80 °C (heat gun). The solvent was then removed in vacuo.
  • the solid was extracted with CH2CI2 (50 mL) and the solution filtered over a plug of Celite. After washing the Celite with 4 x 15 mL CH2CI2, the solvent was removed in vacuo from the filtrate. The solid was dissolved in 15 mL of CH2CI2, filtered and over filtrate a layer of hexane (40 mL) was slowly added.
  • Ligands B-C 1-Methyl-2-(bis-3 ⁇ 5'-trifluoromethylphenyl)indene (Ligand B), and 3-methyl-2-(bis-3',5'-trifluoromethylphenyl)indene (Ligand C)
  • Metallocene 6 (2-Phenylindenyl)(1-methyl-2-phenylindenyl) zirconium dichloride
  • Butyllithium (2 5 M in hexane, 0 43 mL, 1 08 mmol) was added via syringe to the solution of 1 -methyl-2-phenyl ⁇ ndenyl (212 mg, 1 029 mmol) in diethyl ether (25 mL) at -78 °C The resulting light yellow solution was allowed to warm to room temperature and stirred for additional 30 mm The ether was removed in vacuo to yield a white powdery solid, which was combined with solid (2- phenyi ⁇ ndenyl)z ⁇ rcon ⁇ um trichloride (400 mg, 1 029 mmol) and toluene (50 mL) The resulting suspension was stirred for 24 h at room temperature Gradually the solids dissolved to give a yellow turbid solution The mixture was filtered through a
  • Metallocene 7 (2-Phenylindenyl)(1-methyl-2-(bis-3',5'-trifluoromethylphenyl) indenyl) zirconium dichloride
  • Butyllithium (2.5 M in hexanes, 0.43 mL, 1.08 mmol) was added to the pale yellow solution of 1-methyl-2-(bis-3',5'-trifluoromethylphenyl)indene (352 mg, 1.029 mmol) in diethyl ether (20 mL) at -78 °C via syringe. The resulting yellow solution was allowed to warm to room temperature and stirred for additional 30 min. Ether was removed in vacuo to yield a pale yellow solid which was washed with pentane (20 mL) and combined with solid (2-phenylindenyl)zirconium trichloride (400 mg, 1.029 mmol) and toluene (50 mL).
  • Metallocene 8 (2-(3',5'-Trifluoromethy lphenyl)indenyl)(1 -methyl-2- phenylindenyl) zirconium dichloride
  • Butyllithium (2 5 M in hexanes, 0 55 mL, 1 38 mmol) was added to the solution of 1-methyl-2-phenyl ⁇ ndene (277 mg, 1 31 mmol) in diethyl ether (25 mL) at -78 °C via syringe
  • the resulting light yellow solution was allowed to warm to room temperature, stirred for an additional 15 mm, and the ether was removed in vacuo to yield a white powdery solid which was combined with solid (2-(b ⁇ s-3',5'- t ⁇ fluoromethylphenyl) ⁇ ndenyl) zirconium trichloride Me3S ⁇ NMe2 (695 mg, 1 31 mmol) and toluene (40 mL) at 0 °C The resulting dark green solution was allowed to warm to room temperature and stirred for 40 h during which time the color of the solution gradually turned lemon-yellow The turbid solution was filtered through a glass frit packed with Ce
  • Metallocene 9 ⁇ -(S ⁇ '-Trifluoromethylpheny indenylHI-methyl-Z-fbis-S'. ⁇ '- trifluoromethylphenyl) indenyl) zirconium dichloride
  • the solid was then combined with solid (2- (b ⁇ s-3',5'-t ⁇ fiuoromethylphenyl) ⁇ ndenyl) zirconium trichloride Me3S ⁇ NMe2 (508 mg, 0 958 mmol) and toluene (50 mL) and the reaction mixture was stirred for 40 h at
  • Metallocene 10 Bis(2-(bis-3,5-terf-butyl-4-methoxyphenyl) indenyl) zirconium dichloride
  • Copolymer composition and monomer sequence distribution were determined using c NMR spectroscopy Copolymer samples (180-300 mg) were dissolved in 2 5 mL of o-d ⁇ chlorobenzene/10 vol % benzene-dQ in 10 mm tubes 13 C NMR spectra were recorded at 75 425 MHz on a Va ⁇ an UI 300 spectrometer at 100 °C using 10 mm sample tubes Samples were prepared in 1 ,2- dichlorobenzene containing about 0 5 mL d6-benzene and approximately 5 mg of chrom ⁇ um(lll) acetylacetonate to reduce T1 spin relaxation times Spectra were acquired using pulse repetition intervals of 5 s and gated proton decoupling
  • the monomer feed ratio (X e /Xh) was calculated using an equation reported in Spitz et al , Eur Polym J , 1979, v 85, pp 441-4 for the solubility of ethylene in 1- hexene Determination of copolymer composition (mol %E) and sequence distribution were carried out using the method of Cheng (Polym Bull , 1991 , v.26, 325) The triad distributions for commercial elastomers (ENGAGETM 8200 and EXACTTM 4033) were calculated by methods outlined by Randall (Macromol Sci Rev Macromol Chem Phys , 1989, v C29, pp 201-317)
  • the glass transition, melting points and heats of fusion were determined by differential scanning calorimetry using a Perkm-Elmer DSC-7
  • the DSC scans were obtained by first heating copolymer samples to 200 °C for 10 mm, cooling them to 20 °C at 20 °C per minute, aging them at room temperature for 24 h and then reheating from 0 °C to 200 °C at 20 °C/m ⁇ n All DSC values in the tables are reheat values Scans to determine the glass transition temperature were obtained by cooling the sample to -150 °C and then heating to 0 °C at 40 °C/m ⁇ n Two samples of each polymer were run to ensure that the DSC measurements were reproducible Density was measured by a gradient column technique in which a piece of molded specimen was allowed to sink to an equilibrium level in an isopropyl alcohol/water column The float level of the specimen was compared to the float level of glass beads of known density
  • Reactivity ratios, r E and r H , for ethyl and hexene insertion were calculated from diad distribution in 13 C NMR data
  • the r E and r H are 2 5 ⁇ 0 2 and 0 24 ⁇ 0 03, respectively These values compare to typical r E 's of 5-18 and r H 's of 0 03 to 0 18 for polymers made from other catalysts reported in Table 2
  • hafnium- containmg metallocene catalysts preferentially insert 1 -hexene to a greater proportion than observed in comparable zirconium-containing metallocene catalysts
  • Comparative Run T is a commercial Ethylene/Octene Elastomer obtained from Dow (Engage 8200- ⁇ )
  • Comparative Run U is an Ethylene/Butene Elastomer obtained from Exxon (Exact 4033- r )
  • Comparative Run V is a polypropylene elastomer as described in Waymouth et al. US 5,594,080.
  • T m range (°C) 23-130 16-116 11-117 20 - 70 20 - 70 40-160
  • polymers of the present invention and the polymerization catalysts and processes by which the polymers are produced will have wide applicability in industry, inter alia, as elastomers having higher melting points than currently available elastomers, as thermoplastic materials, and as components for blending with other polyolefins for predetermined selected properties, such as raising the melting point of the blend
  • typical polymers of this invention while they have degrees of crystallmity lower than (Examples 5,6,8), or similar to (Examples 20,21) that of Dow's Engage 8200 tm and EXXON's 4033 tm , they have a broader melting point range that extends to higher temperatures, e g , to 130°C, and above
  • compositional homogeneity of copolymers of this invention was investigated by extracting the copolymers in boiling solvents such as ether and hexanes Copolymers were extracted sequentially into solvents of increasing boiling point to separate components of different molecular weight and crystallmity
  • the solvent soluble material was precipitated in stirring methanol and then dried in a vacuum oven at 40 °C The solvent-insoluble material was dried in the vacuum oven while still in the extraction thimble The process was then repeated on the solvent insoluble material with higher boiling solvents until all the material dissolved
  • the heptane extraction was performed first The heptane soluble material was then extracted with diethyl ether
  • Supercritical Fluid Fractionation The solubility of a polymer in a typical organic solvent depends on the identity of the solvent and temperature Higher molecular weight and more highly crystalline components tend to dissolve at reflux in higher boiling solvents Supercritical fluids have an added advantage in that the solubility of the polymer can be tuned by the pressure of the system As pressure is increased, components higher in molecular weight and crystallmity will dissolve This unique feature of supercritical fluids can be exploited to separate polyolefin homo- and copolymers into well-defined fractions Supercritical fluid fractionation techniques have been successfully applied to the fractionation of linear low density polyethylenes according to molecular weight and degree of short chain branching An ethylene-1 -hexene copolymer containing 90 mol %E (See Example 19, below) was fractionated using a supercritical fluid extraction technique Fractionation of the copolymer using supercritical propane was performed as follows The copolymer sample was cut into small pieces and distributed in the fractionation chamber over surface area enhancing packing Irganox 1010' (a
  • the DSC profiles of all the fractions exhibited broad, bimodai melting transitions.
  • the average molecular weights (M v ) of representative fractions were calculated from the intrinsic viscosities of the materials.
  • the Results are shown in Table 6
  • copolymerizations were performed in the presence of hydrogen which will lower polymer molecular weight. Three polymerizations were performed under identical conditions in which two were carried out in the presence of hydrogen
  • the polymerizations were conducted to prepare ethylene-1 -hexene copolymers containing 10 mol % hexene in the presence of hydrogen for molecular weight control. Polymerizations were conducted as described above using Catalyst 4 with MAO except that in Examples 20 and 21 , 2.5 mmol and 5.0 mmol of hydrogen were added to the batch polymerization reactor, respectively. Properties of the resulting copolymers are shown in Tables 7 and 8. Since the concentration of hydrogen in the batch reactor decreased during the polymerization, the polydispersities were high since polymers of differing molecular weights will be formed as the hydrogen concentration decreases.
  • the molecular weights of the copolymers were lowered dramatically when hydrogen was introduced to the system.
  • the polydispersities of the copolymers were higher for materials prepared in the presence of hydrogen.
  • the crystallinity of the copolymers increased substantially as the amount of hydrogen in the system increased.
  • Heptane Soluble 94 90 24-123 30, 40, 95, 112 58.8
  • the material was extracted with heptane for 24 h c
  • the material was extracted with heptane for 72 h d
  • Ethylene- ⁇ -olefin copolymers can be fractionated in situ by DSC by subjecting the material to a series of isothermal crystallization steps beginning in the melt and proceeding at successively lower temperatures. Because uninterrupted ethylene sequences of variable length form crystals of differing sizes and melting points, this procedure separates the DSC melting profile into a series of peaks which correspond to sections of the polymer with different degrees of short chain branching The ethylene-1 -hexene copolymer of Ex.
  • the ether insoluble/heptane soluble fraction comprised 60% of this copolymer.
  • This solvent fraction exhibits a maximum peak melting temperature approximately 20 °C higher than the random copolymers considered by Mandelkern. This suggests that this fraction contains long crystallizable sequences. As this fraction is soluble in heptane the crystallizable sequences are not derived from an ethylene homopolymer. These results indicate that at least 60% of this copolymer exhibits a blocky character.
  • a high molecular weight copolymer prepared with metallocene 4 and containing 79 mol %E (M w -1 ,000,000; Example 7, Table 5) was also compared to the random copolymers reported by Mandelkern ( Figure 6).
  • the hexanes soluble portion of the material exhibits a maximum peak melting temperature over 50 °C higher than a random copolymer with identical composition.
  • the THF and heptane soluble portions of this copolymer also exhibit melting temperatures that are higher than expected for a random copolymer.
  • inventive copolymers illustrate an ethylene-1 -hexene copolymer having a broad melting transition( ⁇ 100°C), a relative high polydispersity (3.5-3.7), a high upper peak melting temperature, and a narrow composition distribution.
  • the melting transition is bimodai as measured by DSC.
  • Ethylene-1 -hexene copolymer was made in a 1 -liter stirred autoclave reactor which was heated to 90 °C and purged with nitrogen. The reactor then was charged with isobutane (750ml) and tri-isobutylaluminium (3.7ml of 1 M solution in hexanes, supplied by Aldrich), and temperature adjusted to 70°C. After 1 hour, the reactor was charged with 1 -hexene (dry, deoxygenated; 10ml), and ethylene (7.3 bar).
  • copolymers of the invention have wide industrial applicability for use in film and fiber formation, cast extruded and smolded plastic products ranging from thermoplastic plastomers to elastomers.
  • Copolymer produced according to the method of this invention may be formed into pellets by melt extrusion and chopping, which then may be used to form useful articles such as extruded pipe, molded fittings and containers.
  • Copolymers of this invention may be combined with effective amounts of typical polymer additives known to the art such as heat and uv stabilizers, anti-oxidants, acid scavengers, anti-static agents, and the like.
  • the copolymers may be combined with colorants and fillers such as glass fiber and talc.
  • Products made from the copolymers of this invention may be formed by techniques known to the art, such as casting, pressing, blowing, and extruding. Films formed from the copolymers may have thicknesses range from about 0.1 mil (.00254mm) to 100 mil (2.54mm) or more. Typical film thickness may be about 0.25 mil (.00635mm) to about 50 mil (1.27mm) and preferably about 0.5 mil (.0127mm) to 20 mil (.508mm). Typical films show improved optical properties such as reduced haze and increased clarity compared to typical linear low density polyethylenes. Other useful articles may be manufactured from the copolymers of this invention by conventional techniques such as molding or extrusion.

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Abstract

Copolymère d'éthylène et d'au moins un comonomère contenant au moins 4 atomes de carbone, qui est caractérisé par une polydispersité supérieure à 2, une large transition du point de fusion telle que mesurée par l'analyse calorimétrique différentielle à compensation de puissance, et une répartition étroite de la composition. Des copolymères éthylène/C4+ peuvent également présenter au moins un point de fusion maximal supérieur au point de fusion maximal d'un copolymère statistique ayant la même composition d'unités monomères. Ces copolymères sont obtenus par mise en contact d'éthylène et d'un comonomère dans des conditions de polymérisation en présence d'un système de fluxion catalyseur approprié.
PCT/US1999/015518 1999-01-08 1999-07-08 Copolymeres d'ethylene a repartition etroite de la composition et a temperatures de fusion elevees, et procedes de production desdits copolymeres WO2000040625A1 (fr)

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AU49793/99A AU4979399A (en) 1999-01-08 1999-07-08 Ethylene copolymers with narrow composition distribution and high melting temperatures, and methods of production thereof
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001072856A1 (fr) * 2000-03-30 2001-10-04 Atofina Research Polyethylene metallocenique pour recipients en plastique brillants
US7279536B2 (en) 2002-09-20 2007-10-09 Exxonmobil Chemical Patents Inc. Polymer production at supercritical conditions
US7319125B2 (en) 2002-09-20 2008-01-15 Exxonmobil Chemical Patents Inc. Supercritical polymerization process and polymers produced therefrom
US7910679B2 (en) 2007-12-20 2011-03-22 Exxonmobil Research And Engineering Company Bulk homogeneous polymerization process for ethylene propylene copolymers
US7910637B2 (en) 2007-09-13 2011-03-22 Exxonmobil Research And Engineering Company In-line blending of plasticizers with a base polymer
US7928162B2 (en) 2007-09-13 2011-04-19 Exxonmobil Research And Engineering Company In-line process for producing plasticized polymers and plasticized polymer blends
US7994237B2 (en) 2007-12-20 2011-08-09 Exxonmobil Research And Engineering Company In-line process to produce pellet-stable polyolefins
US8080610B2 (en) 2007-03-06 2011-12-20 Exxonmobil Research And Engineering Company Monomer recycle process for fluid phase in-line blending of polymers
US8138269B2 (en) 2007-12-20 2012-03-20 Exxonmobil Research And Engineering Company Polypropylene ethylene-propylene copolymer blends and in-line process to produce them
US8143352B2 (en) 2006-12-20 2012-03-27 Exxonmobil Research And Engineering Company Process for fluid phase in-line blending of polymers

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR112016028132B1 (pt) * 2014-05-30 2022-04-19 Bridgestone Corporation Catalisador de complexo metálico e métodos de polimerização usando os mesmos

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995004761A1 (fr) * 1993-08-06 1995-02-16 Exxon Chemical Patents Inc. Catalyseurs de polymerisation, leur fabrication et utilisation
WO1995025757A1 (fr) * 1994-03-24 1995-09-28 The Board Of Trustees Of The Leland Stanford Junior University Polymeres olefiniques stereosequences elastomeres thermoplastiques, procedes de production associes et catalyseurs a base d'alliage organometallique
EP0743324A2 (fr) * 1995-05-16 1996-11-20 Union Carbide Chemicals & Plastics Technology Corporation Production de polyéthylène utilisant des métallocènes stéréoisomériques
EP0812862A2 (fr) * 1986-09-24 1997-12-17 Mitsui Petrochemical Industries, Ltd. Procédé de polymérisation d'oléfines
US5824618A (en) * 1991-06-27 1998-10-20 Nippon Oil Co., Ltd. Catalyst components for polymerization of olefins
EP0926169A2 (fr) * 1997-12-25 1999-06-30 Mitsui Chemicals, Inc. Copolymére d'éthylène/alpha-oléfine et procédé pour sa préparation
WO1999035171A1 (fr) * 1998-01-09 1999-07-15 The Board Of Trustees Of The Leland Stanford Jr. University Elastomeres copolymeres polyolefiniques a point de fusion eleve, catalyseurs et procedes de synthese

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0812862A2 (fr) * 1986-09-24 1997-12-17 Mitsui Petrochemical Industries, Ltd. Procédé de polymérisation d'oléfines
US5824618A (en) * 1991-06-27 1998-10-20 Nippon Oil Co., Ltd. Catalyst components for polymerization of olefins
WO1995004761A1 (fr) * 1993-08-06 1995-02-16 Exxon Chemical Patents Inc. Catalyseurs de polymerisation, leur fabrication et utilisation
WO1995025757A1 (fr) * 1994-03-24 1995-09-28 The Board Of Trustees Of The Leland Stanford Junior University Polymeres olefiniques stereosequences elastomeres thermoplastiques, procedes de production associes et catalyseurs a base d'alliage organometallique
US5594080A (en) * 1994-03-24 1997-01-14 Leland Stanford, Jr. University Thermoplastic elastomeric olefin polymers, method of production and catalysts therefor
EP0743324A2 (fr) * 1995-05-16 1996-11-20 Union Carbide Chemicals & Plastics Technology Corporation Production de polyéthylène utilisant des métallocènes stéréoisomériques
EP0926169A2 (fr) * 1997-12-25 1999-06-30 Mitsui Chemicals, Inc. Copolymére d'éthylène/alpha-oléfine et procédé pour sa préparation
WO1999035171A1 (fr) * 1998-01-09 1999-07-15 The Board Of Trustees Of The Leland Stanford Jr. University Elastomeres copolymeres polyolefiniques a point de fusion eleve, catalyseurs et procedes de synthese

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001072856A1 (fr) * 2000-03-30 2001-10-04 Atofina Research Polyethylene metallocenique pour recipients en plastique brillants
EP1593696A3 (fr) * 2000-03-30 2006-01-04 Total Petrochemicals Research Feluy Polyéthylène métallocénique pour recipients en plastique brillants
US7279536B2 (en) 2002-09-20 2007-10-09 Exxonmobil Chemical Patents Inc. Polymer production at supercritical conditions
US7319125B2 (en) 2002-09-20 2008-01-15 Exxonmobil Chemical Patents Inc. Supercritical polymerization process and polymers produced therefrom
US7354979B2 (en) 2002-09-20 2008-04-08 Exxonmobil Chemical Patents Inc. Polymer production at supercritical conditions
US8143352B2 (en) 2006-12-20 2012-03-27 Exxonmobil Research And Engineering Company Process for fluid phase in-line blending of polymers
US8080610B2 (en) 2007-03-06 2011-12-20 Exxonmobil Research And Engineering Company Monomer recycle process for fluid phase in-line blending of polymers
US7910637B2 (en) 2007-09-13 2011-03-22 Exxonmobil Research And Engineering Company In-line blending of plasticizers with a base polymer
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AU4979399A (en) 2000-07-24
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EP1062257A1 (fr) 2000-12-27

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