WO2013158225A1 - Compositions de polyoléfine et leurs procédés de production - Google Patents

Compositions de polyoléfine et leurs procédés de production Download PDF

Info

Publication number
WO2013158225A1
WO2013158225A1 PCT/US2013/029036 US2013029036W WO2013158225A1 WO 2013158225 A1 WO2013158225 A1 WO 2013158225A1 US 2013029036 W US2013029036 W US 2013029036W WO 2013158225 A1 WO2013158225 A1 WO 2013158225A1
Authority
WO
WIPO (PCT)
Prior art keywords
polystyrene
bis
polyethylene
ruthenium
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2013/029036
Other languages
English (en)
Inventor
Mun F. TSE
Aspy K. Mehta
Joann M. Canich
Matthew W. Holtcamp
John R. Hagadorn
Charles J. Ruff
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Chemical Patents Inc
Original Assignee
ExxonMobil Chemical Patents Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US13/449,939 external-priority patent/US8809456B2/en
Application filed by ExxonMobil Chemical Patents Inc filed Critical ExxonMobil Chemical Patents Inc
Publication of WO2013158225A1 publication Critical patent/WO2013158225A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes

Definitions

  • This invention relates to styrenic modifiers for linear polyolefins.
  • PE Polyethylene
  • HDPE high density polyethylene
  • MDPE medium density polyethylene
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • VLDPE very low density polyethylene
  • UHMWPE ultra high molecular weight polyethylene
  • ULMWPE or PE-WAX ultra low molecular weight polyethylene
  • M w weight-average molecular weight
  • M w /M n molecular weight distribution
  • M w and MWD control PE melt processability.
  • Low M w leads to a low melt viscosity, resulting in fast processing and less energy consumption.
  • low M w tends to decrease mechanical properties, so applications which rely on good mechanical properties, such as film blowing, typically require polymers with bimodal MWDs.
  • LDPE is traditionally the highest volume resin for blown films.
  • an important feature in the film blowing process is its ability to generate a high degree of drawdown so that the gauge of the final film is much thinner than the die gap.
  • this is limited by the strength of the melt in the bubble. If the nip roll speed is too high, the tensile stress in the bubble will exceed the cohesive strength of the melt, resulting in a rupture of the blown film.
  • LLDPE which has similar low amount of crystallinity as LDPE, began to replace LDPE in the 1980s.
  • LLDPE having lower melt strength but higher drawn speed to break than LDPE, may be more easily drawn down than LDPE. Therefore, a thinner LLDPE film can be blown with the same strength as the LDPE film or a LLDPE film is stronger having the same thickness as the LDPE film.
  • SCB short chain branching
  • Traditional LLDPEs contain no long chain branching (LCB).
  • LLDPE is more viscous at the high shear rates when processed in the extruder and the die than LDPE, which contains a certain amount of LCB.
  • the more viscous LLDPE will result in increased screw torque, barrel wear, and melt temperature, and more frequent occurrence of undesirable sharkskin at the die exit.
  • LLDPE shows lower extensional stresses at low strain rates occurring in the molten tube and bubble inflation regions, rendering a higher chance of bubble instability.
  • the narrow MWDs of mLLDPEs (LLDPEs made using a metallocene catalyst) make them even more difficult to process than conventional LLDPEs.
  • This invention relates to methods for producing an alkene terminated polystyrene, comprising: contacting a styrenic block copolymer and an alkene in the presence of a metathesis catalyst under conditions sufficient to produce an alkene terminated polystyrene having an unsaturation functionality of at least 0.7 and a MWD of about 1.5 or less.
  • This invention further relates to methods for producing a functionalized polymer, comprising: contacting a styrenic block copolymer and ethylene in the presence of a metathesis catalyst under conditions sufficient to produce a vinyl terminated polystyrene having an unsaturation functionality of at least 0.7 and a MWD of about 1.5 or less; and grafting the vinyl terminated polystyrene to a polyolefin to form a polyolefin/polystyrene graft copolymer.
  • the invention further relates to methods for producing a functionalized polymer, comprising: contacting a styrenic block copolymer and ethylene in the presence of a metathesis catalyst under conditions sufficient to produce a vinyl terminated polystyrene having a functionality of at least 0.7 and a MWD of about 1.5 or less; and contacting the vinyl terminated polystyrene with ethylene monomer in the presence of a polymerization catalyst system to form a polyethylene/polystyrene copolymer.
  • the invention yet further relates to polyethylene blend compositions, comprising: (i) 99.0 wt% or less of a linear polyethylene having a density of at least 0.910 g/cm 3 ; and (ii) at least 1.0 wt% of a polyethylene/polystyrene graft copolymer comprising from about 70 wt% to about 98 wt% polyethylene and from about 2 wt% to about 30 wt% polystyrene.
  • Figure 1 depicts the GPC curves of SBS, VTPS-1 and VTPS-2 used in the Examples, where SBS is styrenic block copolymer, VTPS-1 is vinyl terminated polystyrene 1 and VTPS- 2 is vinyl terminated polystyrene 2.
  • Figure 2 depicts the two-dimensional HSQC (heteronuclear single-quantum correlation spectroscopy) NMR spectrum of the olefinic region of VTPS-2.
  • Figure 3 depicts the van Gurp-Palmen plots of certain blend components used in the Examples.
  • Figure 4 depicts the complex viscosity versus frequency plots of the blend components plotted in Figure 3.
  • Figure 5 depicts the van Gurp-Palmen plots of an mLLDPE and its blends with 10 wt% of the PE/PS graft copolymer (PE-g-PS) or the HDPE/PS blend (HDPE/PS), where PS is polystyrene, as used in the Examples.
  • PE-g-PS PE/PS graft copolymer
  • HDPE/PS HDPE/PS blend
  • Figure 6 depicts the complex viscosity versus frequency plots of the blend components plotted in Figure 5.
  • Figure 7 depicts the stress-strain curves of mLLDPE and mLLDPE containing 10 wt% of PE-g-PS, as used in the Examples.
  • Figure 8 depicts the stress-strain curves of mLLDPE and mLLDPE containing 10 wt% of HDPE/PS.
  • Figure 9 depicts the van Gurp-Palmen plots of PE-g-PS to the other polymers.
  • Figure 10 depicts the complex viscosity versus frequency plots of the polymers plotted in Figure 9, where DCP is dicumyl peroxide.
  • Figure 11 depicts the van Gurp-Palmen plots of mLLDPE and mLLDPE blended with
  • Figure 12 depicts the complex viscosity versus frequency plots of polymers plotted in Figure 11.
  • a blend of LLDPE preferably mLLDPE
  • a small amount at least 1 wt%, preferably about 1 wt% to 20 wt%
  • these polyethylene blend compositions have improved elasticity and shear thinning in the melt state, compared to the neat polyethylene.
  • the highly branched PE composition comprises a polyethylene/polystyrene graft copolymer.
  • the inventors have also discovered methods of making a vinyl terminated polystyrene with high unsaturation functionality (at least 0.7) and a narrow MWD (1.5 or less), which may be functionalized by grafting to a polyethylene to produce a polyethylene/polystyrene graft copolymer useful in the blend of LLDPE disclosed herein. These compositions, polymers, and methods of making them are discussed further herein.
  • linear polyethylene and “linear ethylene polymer” are used interchangeably and refer to a polyethylene having a branching index (g') of 0.98 or more, preferably 0.99 or more, preferably 1.0 (1.0 being the theoretical limit of g').
  • Branching index (g') is determined as described in U.S. Patent Application Publication No. 2006/0173123, particularly pages 24-25. In the event there is a conflict between the size exclusion chromatography method described in U.S. 2006/0173123 and the size exclusion chromatography method described below, the method described in U.S. 2006/0173123 shall be used for determination of g'.
  • a “metallocene polyethylene” or an “mPE” is an ethylene polymer having a CDBI (Composition Distribution Breadth Index) of greater than 50%, preferably greater than 60%. CDBI is discussed further below.
  • mLLDPE is an ethylene polymer (preferably a copolymer) having a CDBI of greater than 50% (preferably greater than 60%) and a density of 0.910 to 0.940 g/cm 3 .
  • 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.
  • ethylene content of 35 wt% to 55 wt%
  • the mer unit in the copolymer is derived from ethylene in the polymerization reaction and said derived units are present at 35 wt% to 55 wt%, based upon the weight of the copolymer.
  • a “polymer” has two or more of the same or different mer units.
  • a “homopolymer” is a polymer having mer units that are the same.
  • a “copolymer” is a polymer having two or more mer units that are different from each other.
  • 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.
  • a polymer or polymeric chain comprises a concatenation of carbon atoms bonded to each other in a linear or a branched chain, which is referred to herein as the backbone of the polymer (e.g., polyethylene).
  • the polymeric chain may further comprise various pendent groups attached to the polymer backbone which were present on the monomers from which the polymer was produced. These pendent groups are not to be confused with branching of the polymer backbone, the difference between pendent side chains and both short and long chain branching being readily understood by one of skill in the art.
  • alpha-olefin is an olefin having a double bond at the alpha (or 1-) position.
  • linear alpha-olefin or “LAO” is an olefin with a double bond at the alpha position and a linear hydrocarbon chain.
  • a "polyalphaolefin” or “PAO” is a polymer having at least two mer units.
  • a-olefin includes C2-C20 olefins.
  • An ethylene polymer is a polymer having at least 50 mol% ethylene, with the balance being made up by one or more other hydrocarbon monomers, preferably C3 to hydrocarbon monomers, preferably propylene, butene, hexene, octene, or mixtures thereof.
  • a propylene polymer is a polymer having at least 50 mol% of propylene, with the balance being made up by one or more other hydrocarbon monomers, preferably C2 and/or C4 to hydrocarbon monomers, preferably ethylene, butene, hexene, octene, or mixtures thereof.
  • Mn is number average molecular weight as determined by proton nuclear magnetic resonance spectroscopy ( l ⁇ i NMR) unless stated otherwise, Mw is weight average molecular weight as determined by gel permeation chromatography (GPC), Mz is z average molecular weight as determined by GPC, wt% is weight percent, and mol% is mole percent.
  • GPC gel permeation chromatography
  • Mz is z average molecular weight as determined by GPC
  • wt% is weight percent
  • mol% mole percent.
  • Molecular weight distribution (MWD) is defined to be Mw (GPC) divided by Mn (GPC). Unless otherwise noted, all molecular weight units, e.g., Mw, Mn, Mz, are g/mol.
  • catalyst and “catalyst compound” are defined to mean a compound capable of initiating catalysis.
  • the catalyst may be described as a catalyst precursor, a pre-catalyst compound, or a transition metal compound, and these terms are used interchangeably.
  • a catalyst compound may be used by itself to initiate catalysis or may be used in combination with an activator to initiate catalysis. When the catalyst compound is combined with an activator to initiate catalysis, the catalyst compound is often referred to as a pre-catalyst or catalyst precursor.
  • a "catalyst system” is a combination of at least one catalyst compound, at least optional one activator, an optional co-activator, and an optional support material, where the system can polymerize monomers to polymer.
  • 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.
  • anionic ligand is a negatively charged ligand which donates one or more pairs of electrons to a metal ion.
  • neutral donor ligand is a neutrally charged ligand which donates one or more pairs of electrons to a metal ion.
  • a "scavenger” is a compound that is typically added to facilitate oligomerization or polymerization by scavenging impurities. Some scavengers may also act as activators and may be referred to as co-activators. A co-activator, that is not a scavenger, may also be used in conjunction with an activator in order to form an active catalyst. In some embodiments, a co- activator can be pre-mixed with the catalyst compound to form an alkylated catalyst compound, also referred to as an alkylated invention compound.
  • 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 and ethyl alcohol is an ethyl group substituted with an -OH group.
  • hydrocarbyl radical is defined to be Q to C20 radicals, that may be linear, branched, or cyclic (aromatic or non-aromatic); and may include substituted hydrocarbyl radicals as defined herein.
  • a functional group may comprise a hydrocarbyl radical, a substituted hydrocarbyl radical, or a combination thereof.
  • Substituted hydrocarbyl radicals are radicals in which at least one hydrogen atom has been substituted with a heteroatom or heteroatom containing group, or with atoms from Groups 13, 14, 15, 16, and 17 of the Periodic Table of Elements, or a combination thereof, or with at least one functional group, such as halogen (CI, Br, I, F), R*2, OR*, SeR*, TeR*,
  • halogen CI, Br, I, F
  • the hydrocarbyl radical is independently selected from methyl, ethyl, ethenyl, and isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, dec
  • isomers of saturated, partially unsaturated, and aromatic cyclic structures wherein the radical may additionally be subjected to the types of substitutions described above examples include phenyl, methylphenyl, benzyl, methylbenzyl, naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, and the like.
  • a radical when listed, it indicates that radical type and all other radicals formed when that radical type is subjected to the substitutions defined above.
  • Alkyl, alkenyl, and alkynyl radicals listed include all isomers including, where appropriate, cyclic isomers, for example, butyl includes w-butyl, 2- methylpropyl, 1 -methylpropyl, tert-butyl, and cyclobutyl (and analogous substituted cyclopropyls); pentyl includes n-pentyl, cyclopentyl, 1 -methylbutyl, 2-methylbutyl, 3- methylbutyl, 1 -ethylpropyl, and neopentyl (analogous substituted cyclobutyls and cyclopropyls); and butenyl includes E and Z forms of 1 -butenyl, 2-butenyl, 3-butenyl, 1- methyl-1 -propenyl, l-methyl-2-propenyl, 2-methyl- 1 -propenyl, and 2-methyl-2-propenyl (cyclobuten
  • Cyclic compounds having substitutions include all isomer forms, for example, methylphenyl would include ortho-methylphenyl, meta- methylphenyl, and para-methylphenyl; dimethylphenyl would include 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-diphenylmethyl, 3,4-dimethylphenyl, and 3,5- dimethylphenyl.
  • Me is methyl
  • Ph is phenyl
  • Et is ethyl
  • Pr is propyl
  • iPr is isopropyl
  • n-Pr normal propyl
  • Bu is butyl
  • iBu is isobutyl
  • tBu is tertiary butyl
  • p-tBu is para-tertiary butyl
  • nBu is normal butyl
  • TMS is trimethylsilyl
  • TIBAL is triisobutylaluminum
  • TNOAL is triisobutyl n-octylaluminum
  • MAO is methylalumoxane
  • pMe is para-methyl
  • Ar* is 2,6-diisopropylaryl
  • Bz is benzyl
  • THF is tetrahydrofuran
  • RT is room temperature which is defined as 25°C unless otherwise specified
  • tol is toluene.
  • polymerization zone refers to an area or a reactor vessel where activated catalysts and monomers are contacted and a polymerization reaction takes place. When multiple reactors are used, either in series or parallel configuration, each reactor is considered a separate polymerization zone. For a multi-stage polymerization in both a batch reactor and a continuous reactor, each polymerization stage is a separate polymerization zone.
  • continuous refers to a system that operates without interruption or cessation.
  • a continuous process is one where there is continuous addition to, and withdrawal of reactants and products from, the reactor system.
  • Continuous processes can be operated in steady state, i.e., the composition of effluent remains fixed with time if the flow rate, temperature/pressure and feed composition remain invariant.
  • a continuous process to produce a polymer would be one where the reactants are continuously introduced into one or more reactors and polymer product is continuously withdrawn.
  • All molecular weights (Mn, Mw, and Mz) have units of g/mol. Wt% is weight percent and mol% is mole percent.
  • some embodiments of the present invention provide a polyethylene blend composition, comprising: (i) 99.0 wt% or less of a linear polyethylene having a density of at least 0.910 g/cm 3 ; and (ii) at least 1.0 wt% of a polyethylene/polystyrene graft copolymer comprising from about 70 wt% to about 98 wt% polyethylene and from about 2 wt% to about 30 wt% polystyrene.
  • the blend composition may include about 1 wt% to about 20 wt% of the graft copolymer, or about 5 wt% to about 20 wt%, or about 10 wt% to about 20 wt%, or about 5 wt% to about 15 wt% or about 5 wt% to about 10 wt% of the graft copolymer, based on a total weight of the blend composition.
  • the blend composition may also include about 1 wt% to about 20 wt% of the linear polyethylene, or about 5 wt% to about 20 wt%, or about 10 wt% to about 20 wt%, or about 5 wt% to about 15 wt% or about 5 wt% to about 10 wt% of the linear polyethylene, based on a total weight of the blend composition.
  • the linear polyethylene and the polyethylene/polystyrene graft copolymers are discussed in more detail below.
  • the blend composition may optionally include one or more polymer additives, such as reinforcing and non-reinforcing fillers, scratch resistant agents, plasticizers, antioxidants, heat stabilizers, extender oils, lubricants, antiblocking agents, antistatic agents, anti-fogging agent, waxes, foaming agents, pigments, flame/fire retardants, dyes and colorants, and ultraviolet absorber.
  • polymer additives such as reinforcing and non-reinforcing fillers, scratch resistant agents, plasticizers, antioxidants, heat stabilizers, extender oils, lubricants, antiblocking agents, antistatic agents, anti-fogging agent, waxes, foaming agents, pigments, flame/fire retardants, dyes and colorants, and ultraviolet absorber.
  • Other additives include, for example, blowing agents, vulcanizing or curative agents, vulcanizing or curative accelerators, cure retarders, processing aids, tackifying resins, and other processing aids known in the polymer compound
  • additives may be employed to enhance properties.
  • the blends of the present invention may be modified to adjust the characteristics of the blends as desired.
  • the aforementioned additives may be either added independently or incorporated into an additive masterbatch.
  • Such additives may comprise up to about 70 wt%, more preferably up to about 65 wt%, of the total composition.
  • the blend compositions may also include one or more slip agents or mold-release agents to facilitate moldability, preferably present at 50 ppm to 5000 ppm, preferably 0.01 wt% to 0.5 wt% (100 ppm to 5000 ppm), preferably 0.1 wt% to 0.3 wt% (1000 ppm to 3000 ppm), based upon the weight of the composition.
  • Desirable slip additives include but are not limited to saturated fatty acid amides (such as palmitamide, stearamide, arachidamide, behenamide, stearyl stearamide, palmityl pamitamide, and stearyl arachidamide); saturated ethylene-bis-amides (such as stearamido-ethyl-stearamide, stearamido-ethyl-palmitamide, and palmitamido-ethyl-stearamide); unsaturated fatty acid amides (such as oleamide, erucamide, and linoleamide); unsaturated ethylene-bis-amides (such as ethylene-bis-stearamide, ethylene- bis-oleamide, stearyl-erucamide, erucamido-ethyl-erucamide, oleamido-ethyl-oleamide, erucamido-ethyl-oleamide, oleamido-ethyl-lerucamide
  • Preferred slip additives are unsaturated fatty acid amides, which are available from Crompton (KekamideTM grades) and Croda Universal (CrodamideTM grades). Particularly preferred are the erucamide and oleamide versions of unsaturated fatty acid amides.
  • stearamide is also useful in this invention.
  • Other preferred slip additives include those described in WO 2004/005601 Al .
  • the blend compositions may also include one or more additional polymers.
  • Suitable polymers include one or more thermoplastic resins or thermoplastic elastomers.
  • Exemplary thermoplastic resins include crystalline polyolefins, such as polypropylene and impact copolymers.
  • suitable thermoplastic resins may include copolymers of polyolefins with styrene, such as a styrene/ethylene copolymer.
  • the thermoplastic resins are formed by polymerizing ethylene or alpha-olefins, such as propylene, 1-butene, 1- hexene, 1-octene, 2-methyl-l-propene, 3 -methyl- 1-pentene, 4-methyl-l-pentene, 5-methyl-l- hexene, and mixtures thereof.
  • ethylene or alpha-olefins such as propylene, 1-butene, 1- hexene, 1-octene, 2-methyl-l-propene, 3 -methyl- 1-pentene, 4-methyl-l-pentene, 5-methyl-l- hexene, and mixtures thereof.
  • Copolymers of ethylene and propylene and ethylene and propylene with another alpha-olefin such as 1-butene, 1-hexene, 1-octene, 2-methyl-l- propene, 3 -methyl- 1-pentene, 4-methyl-l-pentene, 5 -methyl- 1-hexene, or mixtures thereof, are also contemplated.
  • alpha-olefin such as 1-butene, 1-hexene, 1-octene, 2-methyl-l- propene, 3 -methyl- 1-pentene, 4-methyl-l-pentene, 5 -methyl- 1-hexene, or mixtures thereof.
  • homopolypropylene, impact, and random copolymers of propylene with ethylene or the higher alpha-olefins such as 1-butene, 1-hexene, 1-octene, 2-methyl-l- propene, 3 -methyl- 1-pentene, 4-methyl-l-pentene, 5 -methyl
  • the homopolypropylene has a melting point of at least 130°C, for example at least 140°C and preferably less than or equal to 170°C, a heat of fusion of at least 75 J/g, alternatively at least 80 J/g, as determined by DSC analysis, and weight average molecular weight (M w ) of at least
  • Comonomer contents for these propylene copolymers will typically be from about 1% to about 30% by weight of the polymer (See, for example, U.S. Patent Nos. 6,268,438; 6,288, 171; and 6,245,856). Copolymers available under the trade name VISTAMAXXTM (ExxonMobil, Houston, Texas) are specifically included. Blends or mixtures of two or more polyolefin thermoplastics such as described herein, or with other polymeric modifiers, are also suitable in accordance with this invention.
  • These homopolymers and copolymers may be synthesized by using an appropriate polymerization technique known in the art, such as, but not limited to, the conventional Ziegler-Natta type polymerizations, and catalysis employing single-site organometallic catalysts including, but not limited to, metallocene catalysts.
  • an appropriate polymerization technique known in the art such as, but not limited to, the conventional Ziegler-Natta type polymerizations, and catalysis employing single-site organometallic catalysts including, but not limited to, metallocene catalysts.
  • the linear polyethylene has a density of at least 0.910 g/cm 3 .
  • the linear polyethylene has a density of 0.940 g/cm 3 or more.
  • the density is in the range of from about 0.910 g/cm 3 to 0.98 g/cm 3 (preferably from 0.915 g/cm 3 to 0.96 g/cm 3 , preferably from 0.915 g/cm 3 to 0.950 g/cm 3 ).
  • the linear polyethylene is an LLDPE or an HDPE.
  • the linear polyethylene may be produced either with conventional Ziegler-Natta catalysts or with metallocene catalysts.
  • the linear polyethylene is a metallocene polyethylene (mPE).
  • mPE metallocene polyethylene
  • the mPE homopolymers or mPE copolymers may be produced using mono- or bis-cyclopentadienyl transition metal catalysts or other metallocene catalysts in combination with an activator of alumoxane and/or a non-coordinating anion in solution, slurry, high pressure, or gas phase.
  • the catalyst and activator may be supported or unsupported and the cyclopentadienyl rings may be substituted or unsubstituted.
  • the mPE polymers can include those containing a small amount of long chain branching (LCB), for example below 5 wt%. Accordingly, in embodiments herein, the linear polyethylene may have less than 5 wt% long chain branching.
  • LLB long chain branching
  • Several commercial products produced with such catalyst/activator combinations are commercially available from ExxonMobil Chemical Company in Baytown, Texas under the tradenames EXCEEDTM and ENABLETM.
  • the polyethylene may be a metallocene LLDPE (mLLDPE), preferably present at 0.5 wt% to 99 wt% of an mLLDPE, more preferably 50 wt% to 99 wt%, more preferably 90 wt% to 99 wt%, based upon the weight of the composition.
  • mLLDPE metallocene LLDPE
  • the linear polyethylene may also be a polymer of an ethylene and at least one alpha- olefin.
  • the alpha-olefin has 3 to 40 carbon atoms, more preferably 5 to 20 carbon atoms and most preferably 5 to 10 carbon atoms.
  • Preferred mLLDPEs are copolymers comprising at least 50 wt% ethylene and having up to 50 wt%, preferably 1 wt% to 35 wt%, even more preferably 1 wt% to 6 wt% of a C3-C40 comonomer (e.g., C 4 , Cg), based upon the weight of the copolymer.
  • Preferred comonomers are butene, hexane, octane and decene.
  • the polyethylene copolymers preferably have an M w /M n of from greater than 1 to 10, preferably from 1.5 to 8, preferably 2 to 7, preferably from 2 to 5. In a preferred embodiment, the M w /M n is from 2.5 to 5.5.
  • the linear polyethylene is an ethylene copolymer having a CDBI of 60% or more.
  • the polyethylene copolymers preferably have a composition distribution breadth index (CDBI) of 60% to 85%, preferably 65% to 85%.
  • CDBI composition distribution breadth index
  • the ethylene copolymer has a density of 0.910 g/cm 3 to 0.935 g/cm 3 and a CDBI of 60% to 85% or more, preferably between 65% and 85%.
  • CDBI Composition Distribution Breadth Index
  • the linear polyethylene has an M w of 50,000 g/mol or more, a g' of 0.95 or more, and an M w /M n of from greater than about 1 to about 10, and comprises from
  • the linear polyethylene is a polymer having a density of 0.910 g/cm 3 or more; an M w of 50,000 g/mol or more (preferably 75,000 g/mol or more, preferably 100,000 g/mol or more); a g' of 0.95 or more (preferably 0.98 or more, preferably 0.99 or more, preferably 1.0); an M w /M n of greater than 1 to 10 (preferably from 1.5 to 8, preferably 2 to 5); and comprises from 50 mol% to 100 mol% ethylene (preferably 65 mol% to 99 mol%, preferably 80 mol% to 97 mol%, preferably 90 mol% to 97 mol%), and from 0 mol% to 50 mol% (preferably from 1 mol% to 35 mol%, preferably 3 mol% to 20 mol%, preferably 3 mol% to 10
  • the polymer can be obtained by a continuous gas phase polymerization using supported catalyst of an activated molecularly discrete catalyst in the substantial absence of an aluminum alkyl based scavenger (e.g., triethylaluminum (TEAL), trimethylaluminum (TMAL), triisobutyl aluminum (TIBAL), tri-n-hexylaluminum (TNHAL) and the like).
  • an aluminum alkyl based scavenger e.g., triethylaluminum (TEAL), trimethylaluminum (TMAL), triisobutyl aluminum (TIBAL), tri-n-hexylaluminum (TNHAL) and the like.
  • the linear polyethylene is a polymer of an ethylene and at least one alpha-olefin having 5 to 20 carbon atoms, where the linear polyethylene has a melt index, MI, (ASTM D 1238, 190°C/2.16 kg) of from 0.1 to 15 (preferably 0.3 to 10); a CDBI of at least 70% (preferably at least 75%), a density of from 0.910 to 0.930 g/cm 3 (ASTM 1505, preferably from 0.915 to 0.927 g/cm 3 ); a haze value (ASTM D 1003) of less than 20 (preferably less than 20 when formed into a film, 0.25 to 70 mils thick); a melt index ratio (MIR, ASTM D 1238 121/12) of from 35 to 80; an averaged modulus (M) of from 20,000 to 60,000 psi (137.9 MPa to 413.7 MPa) and a relation between M and the dart impact strength, DIS, (determined by ASTM D 1709, 26 inch,
  • MI melt
  • DIS > 0.8[100 + exp(11.71 - 0.000268M + 2.183x l0 "9 M 2 )]
  • M is the averaged modulus, as further described in U.S. Patent No. 6,255,426, the contents of which are incorporated in their entirety, including columns 7, line 5 through column 10, line 63.
  • the averaged modulus (M) is the sum of the 1% secant modulus (ASTM D 882) in the machine direction and the transverse direction divided by two.
  • the DIS is from 120 to 1000 g/mil, preferably 150 to 800 g/mil.
  • DIS is determined on a film 0.25 to 7 mil thick.
  • Such polyethylenes are further described in U.S. 6,255,426 which is incorporated by reference herein, including the testing procedure described or cited therein.
  • Polyolefin/polystyrene graft copolymers are derived from alkene terminated polystyrene copolymers (preferably vinyl terminated polystyrene copolymers) and an alpha- olefin, preferably, ethylene or polyethylene. Accordingly, the alkene terminated polystyrene copolymers act as macromonomers.
  • a vinyl terminated polystyrene copolymer (VTPS) has a vinyl group at or near the end of a polystyrene (PS) block. The placement of this vinyl group is due to the cross metathesis of a styrenic block copolymer (SBC) comprising butadiene and ethylene. This cross metathesis reaction may be referred to as a "metathesis depolymerization of SBC".
  • SBC styrenic block copolymer
  • Other olefin monomers in place of ethylene or their mixtures (including mixtures with ethylene)
  • some embodiments of the present invention relate to methods for producing an alkene terminated polystyrene, comprising: contacting a styrenic block copolymer and an alkene in the presence of a metathesis catalyst under conditions sufficient to produce an alkene terminated polystyrene having an unsaturation functionality of at least 0.7 and a MWD of about 1.5 or less.
  • the "unsaturation functionality" (f) is determined for an alkene-terminated polystyrene as follows:
  • ATPS alkene terminated polystyrene
  • W is a measure of the degree of unsaturation, as defined below.
  • Mn(ATPS) is the number average molecular weight of the alkene-terminated polystyrene as determined by GPC-DRI relative to polystyrene standards.
  • the unsaturation functionality is calculated based on the vinyl groups, as follows:
  • VTPS is vinyl terminated polystyrene
  • W is the degree of unsaturation, and is calculated as follows:
  • W [(integrated intensity of region from about 4.8-5.1 ppm)/2]/[(integrated intensity of region from about 6.1 to 7.3)/5].
  • the alkene terminated polystyrene is a vinyl terminated polystyrene and the alkene is ethylene.
  • Vinylidene and vinylene terminated polystyrene copolymers are also within the scope of the present invention. The relative reactivity of these alkene termini may determine their utility for various applications.
  • the styrenic block copolymer comprises butadiene blocks.
  • Suitable styrenic block copolymers include a styrene-butadiene diblock, a styrene-butadiene- styrene triblock, a styrene-butadiene multiblock, a styrene-butadiene star block represented by the formula (SB) n , where S represents a styrenic block, B represents a butadiene block, and n is the number of arms, and blends thereof, and the like.
  • the styrenic block copolymer is a styrene-butadiene-styrene triblock copolymer or blends thereof.
  • the butadiene block is derived essentially from 1,4-butadiene.
  • Useful commercial styrenic block copolymers include VECTORTM 6241 A, available from Dexco Polymers (Houston, TX).
  • the catalyst comprises at least one of group 6 and/or group 8 metals.
  • the metathesis catalyst comprises one or more of ruthenium, tungsten, and molybdenum.
  • the metathesis catalyst comprises ruthenium.
  • the metathesis catalyst is represented by the Formula (A):
  • M is a Group 8 metal, preferably Ru or Os, preferably Ru;
  • X and X 1 are, independently, any anionic ligand, preferably a halogen (preferably CI), an alkoxide or a triflate, or X and X 1 may be joined to form a dianionic group and may form single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non- hydrogen atoms;
  • L and L 1 are, independently, a neutral two electron donor, preferably a phosphine, a cyclic alkyl amino carbene, or a N-heterocyclic carbene, L and L 1 may be joined to form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;
  • L and X may be joined to form a multidentate monoanionic group and may form single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;
  • L 1 and X 1 may be joined to form a multidentate monoanionic group and may form single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;
  • R and R 1 are, independently, hydrogen or to C30 substituted or unsubstituted hydrocarbyl (preferably a Q to C30 substituted or unsubstituted alkyl or a substituted or unsubstituted C4 to C30 aryl);
  • R 1 and L 1 or X 1 may be joined to form single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;
  • R and L or X may be joined to form single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms.
  • the metathesis catalyst is one or more of: 2,6-diisopropylphenylimidoneophylidene molybdenum(VI) bis(t-butoxide), 2,6- diisopropylphenylimidoneophylidene molybdenum(VI) bis(hexafluoro-t-butoxide), 2,6- diisopropylphenylimido neophylidenemolybdenum(VI) bis(trifluoromethanesulfonate) dimethoxyethane adduct, 2,6-diisopropylphenylimidoneophylidene[racemic-
  • the metathesis catalyst is represented by one or more of the following N-heterocyclic carbene or cyclic alkyl amino carbene structures:
  • the VTPS has an unsaturation functionality (f) of at least 0.7 (preferably, at least 0.75, at least 0.80, at least 0.85, at least 0.90, or at least 0.95) and a MWD of about 1.5 or less (preferably MWD of about 1.2 or less).
  • the weight average molecular weight (M w ) of the VTPS is within preferably 15% of the M w of a single styrenic block of the precursor SBS, where the precursor SBS is the SBS before metathesis.
  • the difference between the M w of the VTPS and the M w of a single styrenic block of the precursor SBS is about 2% to 10%.
  • the M w of the VTPS is less than 200,000, preferably less than 100,000, or preferably less than 50,000.
  • the graft copolymer is a polyethylene grafted with a vinyl terminated polystyrene (VTPS).
  • VTPS vinyl terminated polystyrene
  • some embodiments of the present invention relate to methods for producing a functionalized polymer, comprising: contacting a styrenic block copolymer and alpha olefin monomer (preferably ethylene) in the presence of a metathesis catalyst under conditions sufficient to produce a vinyl terminated polystyrene having a functionality of at least 0.7 and a MWD of about 1.5 or less; and grafting the vinyl terminated polystyrene to a polyolefin (preferably polyethylene) to form a polyolefin/polystyrene graft copolymer (preferably polyethylene/polystyrene graft copolymer).
  • a polyolefin preferably polyethylene
  • the vinyl terminated polystyrene can contact with a vinyl terminated polyolefin in the presence of a catalyst comprising one or more group 6 and/or group 8 metals (preferably ruthenium, tungsten, and/or molybdenum) at conditions sufficient to produce a copolymer composition comprising at least 40 wt% of a diblock copolymer of polystyrene and polyolefin, based on the total weight of the copolymer composition.
  • Diblock copolymer means having one mer unit derived from the vinyl terminated polystyrene and another mer unit derived from the polyolefin in the same molecule.
  • the vinyl terminated polystyrene may be grafted to the polyolefin, for example, polyethylene, by reactive blending in the presence of at least one organic peroxide.
  • the VTPS can also react with a vinyl terminated amorphous polypropylene in the presence of a catalyst containing ruthenium, tungsten, or molybdenum at conditions (for example, both polymers dissolved in toluene, reaction performed in an inert atmosphere) sufficient to produce at least 40 wt% of a diblock copolymer of polystyrene and polypropylene.
  • this diblock can be used as a modifier for another homopolymer or copolymer of propylene or as a compatibilizer for the blend of a homopolymer or copolymer of propylene and a styrenic polymer or copolymer.
  • the reactive blending may take place in a mixer, for example a batch mixer
  • BRABENDERTM mixer two roll mill, etc.
  • a continuous mixer single screw extruder, twin screw extruder, etc.
  • This reactive blending also referred to as peroxide grafting, is discussed below.
  • the polyolefin/polystyrene graft copolymer may also be produced by using a suitable metallocene catalyst to copolymerize alpha olefin monomer with the VTPS.
  • a PE/PS graft copolymer is produced.
  • a suitable metallocene catalyst to copolymerize ethylene monomer with the VTPS.
  • the polyolefin/polystyrene graft copolymer can also be produced by the "in-reactor polymer blend" approach.
  • in- reactor polymer blend also known as an "intimate blend” refers to a mixture of polymers produced in one or more polymerization zones in the same polymerization process/system without the need for post polymerization blending or reaction (although the resultant copolymer can undergo post polymerization blending, for example, to incorporate additives, etc.).
  • the metathesis depolymerization of SBC and the copolymerization of alpha olefin (for example, ethylene) and the resulting VTPS are performed sequentially in the same polymerization process/system.
  • Each polymer component in the mixture possesses a unique molecular structure at different times, such as the SBC, the VTPS macromonomer, the propagating polyethylene chain initiated by a metallocene catalyst in the presence of a methylalumoxane coinitiator (activator), and the final PE/PS graft copolymer.
  • the metallocene catalyzed polymerization to produce a polyolefin/polystyrene graft polymer is discussed further below.
  • the resulting polyolefin/polystyrene graft copolymer (preferably, PE-g-PS) by any of the methods described can be added as a styrenic modifier to polyolefin to improve its physical properties.
  • PE-g-PS can be added as a modifier to polyethylene, particularly linear polyethylene, to improve its melt elasticity and processability.
  • polyethylene and "ethylene polymer” are used interchangeably.
  • a particularly preferred process for preparing the polyolefin/polystyrene graft copolymer includes melt blending polyolefin (preferably PE) and VTPS in the substantial absence of a solvent, with a free radical generating catalyst, such as a peroxide catalyst in a shear-imparting reactor, such as an extruder reactor.
  • a free radical generating catalyst such as a peroxide catalyst in a shear-imparting reactor, such as an extruder reactor.
  • One or more single screw and/or multiple screw reactors may be used, preferably twin screw extruder reactors such as co-rotating intermeshing extruders, counter-rotating non-intermeshing extruders, and/or co-kneaders such as those sold by Buss Inc., USA (Carol Stream, IL) are especially preferred.
  • the polyethylene and the VTPS can be combined into an intimate mixture using conventional blending equipment and methods used in the elastomer industry.
  • Suitable equipment includes batch mixers, internal mixers (such as BANBURYTM mixers, commercially available from Farrel Corporation, Ansonia, CT), roll-mills, kneaders, extruders (including combinations of a compounding extruder and a side-arm extruder used directly or indirectly downstream of a polymerization process), static mixers, impingement mixers, and combinations thereof.
  • the components can be first "dry-blended" such as in a tumble-blender and subsequently melt-blended in the blending equipment, or can be combined by direct addition individually into the blending equipment.
  • Useful organic peroxides include but are not limited to: diaryl peroxides, ketone peroxides, peroxydicarbonates, peroxyesters, dialkyl peroxides, hydroperoxides, benzoyl peroxides, lauroyl peroxides, di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, t- butyl peroctoate, p-di(t-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-di(t- butylperoxy)hexane, l, l-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di(t- butylperoxy)hexene-3, t-butyl-peroxy-(cis-3-carboxy)propenoate, l, l
  • Peroxides having a 1 minute half-life at temperatures of less than 200°C are preferred. Blends of peroxides having different activation temperatures can be utilized to more precisely control the grafting process.
  • Peroxides are available from a variety of commercial suppliers, including LUPEROXTM from Arkema (France), TRIGONOXTM and PERKADOXTM from Akzo Nobel (Netherlands), and VAROXTM from R.T. Vanderbilt (Norwalk, CT), either as a liquid product, a solid product or as a concentrated assay on an inorganic support.
  • the organic peroxide is dicumyl peroxide.
  • a preferred sequence of events used for the grafting reaction comprises the steps of melting the polymers, introducing the peroxide catalyst, and venting the unreacted monomer and by-products resulting from the peroxide decomposition.
  • the grafting reaction is preferably carried out at a temperature selected to minimize or avoid rapid vaporization and consequent losses of the peroxide catalyst and to have residence times about 6 to 7 times the half life time of the peroxide.
  • the polyethylene is preferably grafted with the VTPS at high temperature. Suitable temperatures range from a low of about 50°C to a high of about 350°C. The temperature can also range from a low of about 75°C, 100°C, or 125°C, to a high of about 200°C, 250°C, or 300°C.
  • the peroxide can be dissolved at an approximate 10% concentration in a mineral oil whereas the polyolefin (preferably PE) and the VTPS are preferably fed neat.
  • the peroxide catalyst is preferably used in a ratio of from 0.00001 wt% to 100 wt%, more preferably from 0.1 wt% to 10 wt%, based on the weight of the VTPS.
  • the polyolefin/polystyrene graft copolymer (for example, PE-g-PS) can also be produced using any appropriate polymerization techniques known in the art.
  • Polymerization methods include high pressure, slurry, gas, bulk, suspension, supercritical, or solution phase, or a combination thereof, using a single-site metallocene catalyst system.
  • the catalysts can be in the form of a homogeneous solution, supported, or a combination thereof.
  • Polymerization may be carried out by a continuous, a semi-continuous or batch process and may include use of chain transfer agents, scavengers, or other such additives as deemed applicable.
  • the in-reactor blend compositions can be produced in a single reaction vessel or zone with at least two catalysts, which are added at two different times.
  • the catalyst capable of performing metathesis depolymerization of SBC based on butadiene is added first to this SBC dissolved in a suitable solvent in the reaction zone to produce the VTPS in the presence of alkene, preferably ethylene.
  • alkene preferably ethylene
  • at least one metallocene catalyst together with a methylalumoxane (MAO) activator is added.
  • Copolymerization of alkene monomer (preferably ethylene) with VTPS is carried out to produce the polyolefin/polystyrene (preferably PE/PS graft copolymer).
  • Methylalumoxane deactivates the metathesis catalyst after the VTPS is produced.
  • the remaining methylalumoxane acts as an activator for the metallocene catalyst(s) to copolymerize the alkene with the VTPS.
  • the metathesis and metallocene catalysts can be fed into the reaction zone as a homogeneous catalyst solution through separated feed lines.
  • the metathesis and/or metallocene catalyst(s) can be also supported on a support material.
  • the polyolefin/polystyrene graft copolymer (for example, PE-g-PS) can be produced in a single reaction zone with at least one catalyst to copolymerize alpha olefin monomer (for example, ethylene) with VTPS.
  • the catalyst(s) can be fed into the reactor as a homogeneous catalyst solution through separated feed lines.
  • the catalyst(s) for copolymerization can be also supported on a support material.
  • a metallocene catalyst system is preferred to copolymerize the ethylene monomer with the VTPS macromonomer to produce the polyethylene/polystyrene graft copolymer.
  • Suitable metallocene precatalysts are those selected from formulas (I), (II), (III), and (IVa) (described below) which when used with suitable activators, are capable of producing a polyethylene at commercially attractive temperatures of from about 50°C to about 150°C.
  • Two or more metallocene catalysts can be selected which produce polymers having different molecular weights. This results in a broader molecular weight distribution.
  • Metallocene catalyst compounds are generally described throughout in, for example, METALLOCENE-BASED POLYOLEFINS, Vol. 1 & 2 (John Scheirs & W. Kaminsky eds., John Wiley & Sons, 2000); G. G. Hlatky in COORDINATION CHEM. REV. Vol. 181, pp. 243-296, 1999 and in particular, for use in the synthesis of polyethylene in METALLOCENE- BASED POLYOLEFINS, Vol. 1, pp. 261-377, 2000.
  • the metallocene catalyst compounds as described herein include "half sandwich” and “full sandwich” compounds having one or more Cp ligands (cyclopentadienyl and ligands isolobal to cyclopentadienyl) bound to at least one Group 3 to Group 12 metal atom, and one or more leaving group(s) bound to the at least one metal atom.
  • these compounds will be referred to as "metallocenes” or "metallocene catalyst components” or “metallocene catalysts” or “metallocene pre-catalysts” or “pre-catalysts”.
  • the Cp ligands are typically ⁇ -bonded and/or fused ring(s) or ring systems.
  • the ring(s) or ring system(s) typically comprise atoms selected from the group consisting of Groups 13 to 16 atoms, and more particularly, the atoms that make up the Cp ligands are selected from the group consisting of carbon, nitrogen, oxygen, silicon, sulfur, phosphorous, germanium, boron, aluminum, and combinations thereof, wherein carbon makes up at least 50% of the ring members.
  • the Cp ligand(s) may be selected from the group consisting of substituted and unsubstituted cyclopentadienyl ligands and ligands isolobal to cyclopentadienyl, non-limiting examples of which include cyclopentadienyl, indenyl, fluorenyl, and other structures.
  • Such ligands include cyclopentadienyl, cyclopentaphenanthreneyl, indenyl, benzindenyl, fluorenyl, octahydro fluorenyl, cyclooctatetraenyl, cyclopentacyclododecene, phenanthrindenyl, 3,4- benzofluorenyl, 9-phenylfluorenyl, 8-H-cyclopent[a]acenaphthylenyl, 7H-dibenzofluorenyl, indeno[l,2-9]anthrene, thiophenoindenyl, thiophenofluorenyl, partially hydrogenated versions thereof (e.g., 4,5,6,7-tetrahydroindenyl, or "H 4 Ind", where Ind means indenyl), substituted versions thereof, and heterocyclic versions thereof.
  • Ind means indenyl
  • the metallocenes useful in the present invention may be selected from those including one or two (two, in a more particular embodiment), of the same or different Cp rings selected from the group consisting of cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, and substituted versions thereof.
  • the metal atom "M" of the metallocene catalyst compound may be selected from the group consisting of groups 3 through 12 atoms and lanthanide group atoms in one embodiment; and selected from the group consisting of groups 3 through 10 atoms in a more particular embodiment, and selected from the group consisting of Sc, Ti, Zr, Hf, V, b, Ta, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, and Ni in yet a more particular embodiment; and selected from the group consisting of groups 4, 5, and 6 atoms in yet a more particular embodiment, and from Ti, Zr, Hf atoms in yet a more particular embodiment, and may be Zr in yet a more particular embodiment.
  • the oxidation state of the metal atom "M” may be in the range from 0 to +7 in one embodiment; and in a more particular embodiment, is +1, +2, +3, +4, or +5; and in yet a more particular embodiment is +2, +3, or +4.
  • the groups bound to the metal atom "M” are such that the compounds described below in the formulas and structures are electrically neutral, unless otherwise indicated.
  • the Cp ligand(s) form at least one chemical bond with the metal atom "M” to form the "metallocene catalyst compound".
  • the Cp ligands are distinct from the leaving groups bound to the catalyst compound in that they are not highly susceptible to substitution/abstraction reactions.
  • the one or more metallocene catalyst components of the invention are represented by the formula (I): Cp A Cp B MX n wherein M is as described above; each X is chemically bonded to M; each Cp group is chemically bonded to M; and n is 0, 1, 2, 3, or 4, and either 1 or 2 in a particular embodiment.
  • the ligands represented by Cp A and Cp B in formula (I) may be the same or different cyclopentadienyl ligands or ligands isolobal to cyclopentadienyl, either or both of which may contain heteroatoms and either or both of which may be substituted by a group R.
  • Cp A and Cp B are independently selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, and substituted derivatives of each.
  • each Cp A and Cp B of formula (I) may be unsubstituted or substituted with any one or combination of substituent groups R.
  • Non- limiting examples of substituent groups R as used in formula (I) as well as ring substituents in formulas (II), (III) and (IVa) include groups selected from the group consisting of hydrogen radicals, alkyls, alkenyls, alkynyls, cycloalkyls, aryls, acyls, aroyls, alkoxys, aryloxys, alkylthiols, dialkylamines, alkylamidos, alkoxycarbonyls, aryloxycarbonyls, carbomoyls, alkyl- and dialkyl-carbamoyls, acyloxys, acylaminos, aroylaminos, and combinations thereof.
  • alkyl and aryl substituent groups R associated with formula (I) through (IVa) include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl, phenyl, methylphenyl, tert-butylphenyl groups, and the like, including all their isomers, for example tertiary-butyl, isopropyl, and the like.
  • radicals include substituted alkyls and aryls, such as, for example, fluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromohexyl, chlorobenzyl, and hydrocarbyl substituted organometalloid radicals including trimethylsilyl, trimethylgermyl, methyldiethylsilyl, and the like; halocarbyl-substituted organometalloid radicals including tris(trifluoromethyl)silyl, methylbis(difluoromethyl)silyl, bromomethyldimethylgermyl, and the like; disubstituted boron radicals including dimethylboron, for example; and disubstituted group 15 radicals including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine, group 16 radicals including methoxy, ethoxy, propoxy, phenoxy, methylsulf
  • substituents R include olefins, such as, but not limited to, olefinically-unsaturated substituents including vinyl terminated ligands, for example 3-butenyl, 2-propenyl, 5-hexenyl, and the like.
  • at least two R groups are joined to form a ring structure having from 3 to 30 atoms selected from the group consisting of carbon, nitrogen, oxygen, phosphorous, silicon, germanium, aluminum, boron, and combinations thereof.
  • a substituent group R group such as 1-butanyl, may form a bonding association to the element M.
  • Non-limiting examples of X groups include alkyls, amines, phosphines, ethers, carboxylates, dienes, hydrocarbon radicals having from 1 to 20 carbon atoms; fluorinated hydrocarbon radicals (e.g.,— C ⁇ (pentafluorophenyl)), fluorinated alkylcarboxylates (e.g.,
  • X ligands include groups, such as cyclobutyl, cyclohexyl, methyl, heptyl, tolyl, trifluoromethyl, tetramethylene, pentamethylene, methylidene, methoxy, ethoxy, propoxy, phenoxy, bis(N-methylanilide), dimethylamide, dimethylphosphide radicals, and the like.
  • two or more X's form a part of a fused ring or ring system.
  • the metallocene catalyst component includes those of formula (I) where Cp A and Cp B are bridged to each other by at least one bridging group, (A), such that the structure is represented by formula (II): Cp A (A)Cp B MX n .
  • These bridged compounds represented by formula (II) are known as "bridged metallocenes".
  • Cp A , Cp B , M, X, and n in formula (II) are as defined above for formula (I); and wherein each Cp ligand is chemically bonded to M, and (A) is chemically bonded to each Cp.
  • Non-limiting examples of bridging group (A) include divalent hydrocarbon groups containing at least one Group 13 to 16 atom, such as, but not limited to, at least one of a carbon, oxygen, nitrogen, silicon, aluminum, boron, germanium, tin atom, and combinations thereof; wherein the heteroatom also may be Ci to Ci2 alkyl or aryl substituted to satisfy neutral valency.
  • the bridging group (A) also may contain iron or substituent groups R as defined above (for formula (I)) including halogen radicals.
  • the bridged metallocene catalyst component of formula (II) has two or more bridging groups (A).
  • bridging group (A) include methylene, ethylene, ethylidene, propylidene, isopropylidene, diphenylmethylene, 1 ,2-dimethylethylene, 1,2- diphenylethylene, 1, 1,2,2-tetramethylethylene, dimethylsilyl, diethylsilyl, methyl-ethylsilyl, trifluoromethylbutylsilyl, bis(trifluoromethyl)silyl, di(n-butyl)silyl, di(n-propyl)silyl, di(i- propyl)silyl, di(n-hexyl)silyl, dicyclohexylsilyl, diphenylsilyl, cyclohexylphenylsilyl, t- butylcyclohexylsilyl, di(t-butylphenyl)silyl, di(p-tolyl)silyl, and the corresponding
  • bridging group (A) also may be cyclic.
  • the cyclic bridging groups (A) may be saturated or unsaturated and/or may carry one or more substituents and/or may be fused to one or more other ring structures.
  • the ligands Cp A and Cp B of formula (I) and (II) are different from each other in one embodiment, and the same in another embodiment.
  • the metallocene catalyst components include bridged mono-ligand metallocene compounds (e.g., mono cyclopentadienyl catalyst components).
  • the at least one metallocene catalyst component is a bridged "half-sandwich" metallocene represented by the formula (III): Cp A (A)QMX n wherein Cp A is defined above and is bound to M; (A) is a bridging group bonded to Q and Cp A ; and wherein an atom from the Q group is bonded to M; and n is an integer 0, 1, or 2.
  • any of Cp A , (A) and Q may form a fused ring system.
  • Cp A is selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, substituted versions thereof, and combinations thereof.
  • Q is a heteroatom-containing ligand in which the bonding atom (the atom that is bonded with the metal M) is selected from the group consisting of group 15 atoms and group 16 atoms in one embodiment, and selected from the group consisting of nitrogen, phosphorus, oxygen, or sulfur atom in a more particular embodiment, and nitrogen and oxygen in yet a more particular embodiment.
  • Non-limiting examples of Q groups include amides, alkoxides, alkylamides, arylamides, phosphides, alkylphosphides, arylphosphides, mercapto compounds, carboxylates (e.g., pivalate), carbamates, azenyl, azulene, phosphoryl, phosphinimine, pyrrolyl, pyrozolyl, carbazolyl, and other compounds comprising group 15 and group 16 atoms capable of bonding with M.
  • carboxylates e.g., pivalate
  • carbamates e.g., azenyl, azulene, phosphoryl, phosphinimine, pyrrolyl, pyrozolyl, carbazolyl, and other compounds comprising group 15 and group 16 atoms capable of bonding with M.
  • the at least one metallocene catalyst component may be an unbridged "half sandwich” metallocene represented by the formula (IVa):
  • Cp A is defined as for the Cp groups in (I) and is a ligand that is bonded to M; each J is independently bonded to M; X is a leaving group as described above in (I); n ranges from 0 to 3, and is 0 or 3 in one embodiment; q ranges from 0 to 3; and is 0 or 3 in one embodiment.
  • Cp A is selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, substituted version thereof, and combinations thereof.
  • Non-limiting examples of J include to C 12 carbamates, to C 12 carboxylates (e.g., pivalate), C 2 to C 2Q alkyls, and C 2 to C 2Q heteroallyl moieties.
  • the metallocene catalyst component is one or more as described in U.S. Patent Nos. 5,703,187 and 5,747,406, including a dimer or oligomeric structure, such as disclosed in, for example, U.S. Patent Nos. 5,026,798 and 6,069,213.
  • the metallocene catalyst component is one or more as described in U.S. Patent No. 6,069,213.
  • metallocene catalyst components described above include their structural or optical or enantiomeric isomers (racemic mixture), and may be a pure enantiomer in one embodiment.
  • a single, bridged, asymmetrically substituted metallocene catalyst component having a racemic and/or meso isomer does not, itself, constitute at least two different bridged, metallocene catalyst components.
  • the "metallocene catalyst component" useful in the present invention may comprise any combination of any embodiment described herein.
  • the catalyst system employed in the present process employs an activator preferably selected from alumoxanes, such as methyl alumoxane, modified methyl alumoxane, ethyl alumoxane, z ' so-butyl alumoxane, and the like; neutral activators, such as triphenyl boron, tris-perfluorophenyl boron, tris- perfluoronaphthylboron, tris-perfluorophenyl aluminum, and the like; and ionic activators, such as N,N-dimethylanilinium tetrakis perfluorophenyl borate, triphenyl carbonium tetrakis perfluorophenyl borate, N,N-dimethylanilinium tetrakis perfluoronaphthyl borate, N,N- dimethylanilinium tetrakis perfluor
  • a co-activator is a compound capable of alkylating the transition metal complex, such that when used in combination with an activator, an active catalyst is formed.
  • Co-activators include alumoxanes, such as methyl alumoxane; modified alumoxanes, such as modified methyl alumoxane; and aluminum alkyls, such as trimethyl aluminum, tri-isobutyl aluminum, triethyl aluminum, and tri-isopropyl aluminum.
  • Co-activators are typically only used in combination with neutral activators and ionic activators when the pre-catalyst is not a dihydrocarbyl or dihydride complex.
  • the alumoxane component useful as an activator typically is an oligomeric aluminum compound represented by the general formula (R x -Al-0) n , which is a cyclic compound, or R x (R x -Al-0) n AlR x 2, which is a linear compound.
  • R x is independently a C C2o alkyl radical, for example methyl, ethyl, propyl, butyl, pentyl, isomers thereof, and the like, and "n" is an integer from 1-50. Most preferably, R x is methyl and "n" is at least 4.
  • Methyl alumoxane and modified methyl alumoxanes are most preferred.
  • the pre-catalyst (all pre-catalysts)- to-activator molar ratio is from about 1 :3000 to about 10: 1; alternatively 1 :2000 to 10: 1 ; alternatively 1 : 1000 to 10: 1; alternatively 1 :500 to 1 : 1 ; alternatively 1 :300 to 1 : 1; alternatively 1 :200 to 1 : 1 ; alternatively 1 : 100 to 1 : 1 ; alternatively 1 :50 to 1 : 1 ; alternatively 1 : 10 to 1 : 1.
  • some embodiments select the maximum amount of activator at a 5000-fold molar excess over the pre-catalyst (per metal catalytic site).
  • the preferred minimum activator-to-pre-catalyst- ratio is 1 : 1 molar ratio.
  • NCA NON-COORDINATING ANION
  • non-coordinating anion means an anion that does not coordinate to the catalyst metal cation or that does coordinate to the metal cation, but only weakly.
  • An NCA coordinates weakly enough that a neutral Lewis base, such as an olefinically or acetylenically unsaturated monomer can displace it from the catalyst center.
  • “Compatible” non-coordinating anions are those which are not degraded to neutrality when the initially formed complex decomposes. Further, the anion will not transfer an anionic substituent or fragment to the cation so as to cause it to form a neutral transition metal compound and a neutral by-product from the anion.
  • Non-coordinating anions useful in accordance with this invention are those that are compatible, stabilize the transition metal complex cation in the sense of balancing its ionic charge at +1, and yet retain sufficient liability to permit displacement by an ethylenically or acetylenically unsaturated monomer during polymerization.
  • These types of cocatalysts sometimes use scavengers, such as, but not limited to, tri-z ' so-butyl aluminum, tri-w-octyl aluminum, tri-w-hexyl aluminum, triethylaluminum, or trimethylaluminum.
  • NCA activators at times used in combination with a co-activator may be used in the practice of this invention.
  • discrete ionic activators such as [Me 2 PhNH] [B(C6F 5 )4], [Ph 3 C] [B(C 6 F 5 ) 4 ], [Me 2 PhNH] [B(C 6 H3-3,5-(CF 3 ) 2 ) 4 ], [Ph 3 C] [B(C 6 H3-3,5-(CF 3 ) 2 )4], [NH 4 ] [B(C 6 H 5 ) 4 ], [Me 2 PhNH] [B(C 10 F 7 ) 4 ], [Ph 3 C] [B(C 10 F 7 ) 4 ], or neutral activators, such as B(C6F 5 ) 3 , B(C 1 QF 7 ) 3 , or B(C6H 5 ) 3 can be used (where C ⁇ F 5 is perfluorophenyl, Q0F-7 is perfluorona
  • Preferred co- activators when used, are alumoxanes, such as methyl alumoxane, modified alumoxanes, such as modified methyl alumoxane, and aluminum alkyls, such as tri-isobutyl aluminum, and trimethyl aluminum.
  • NCA activators which may be neutral or ionic, such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, a trisperfluorophenyl boron metalloid precursor, or a trisperfluoronaphthyl boron metalloid precursor, polyhalogenated heteroborane anions (WO 98/43983), boric acid (U.S. Patent No. 5,942,459).
  • NCA activators which may be neutral or ionic, such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, a trisperfluorophenyl boron metalloid precursor, or a trisperfluoronaphthyl boron metalloid precursor, polyhalogenated heteroborane anions (WO 98/43983), boric acid (U.S. Patent No. 5,942,459).
  • neutral NCA activators include tri-substituted boron, tellurium, aluminum, gallium and indium or mixtures thereof.
  • the three substituent groups are each independently selected from alkyls, alkenyls, halogen, substituted alkyls, aryls, arylhalides, alkoxy, and halides.
  • the three groups are independently selected from halogen, mono or multicyclic (including halosubstituted) aryls, alkyls, and alkenyl compounds and mixtures thereof, preferred are alkenyl groups having 1-20 carbon atoms, alkyl groups having 1-20 carbon atoms, alkoxy groups having 1-20 carbon atoms and aryl groups having 3-20 carbon atoms (including substituted aryls). More preferably, the three groups are alkyls having 1-4 carbon groups, phenyl, naphthyl, or mixtures thereof. Even more preferably, the three groups are halogenated, preferably fluorinated, aryl groups. Most preferably, the neutral NCA activator is trisperfluorophenyl boron or trisperfluoronaphthyl boron.
  • Ionic NCA 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 Bl ; 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 USSN 08/285,380, filed August 3, 1994, all of which are herein fully incorporated by reference.
  • Activated ionic catalysts can be prepared by reacting a transition metal compound (pre-catalyst) with a neutral activator, such as B(C6F 6 ) 3 , 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.
  • a neutral activator such as B(C6F 6 ) 3
  • the ionic activator reacts with the transition metal compound (pre- catalyst) to form a cationic transition metal species, an anion, and byproduct(s).
  • the byproducts are defined by the cation associated with the ionic NCA activator used.
  • Compounds useful as an ionic NCA activator 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 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, nitriles, 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)
  • said anion will be sufficiently labile to be displaced by olefinic, diolefinic and acetylenically unsaturated substrates or other neutral Lewis bases, such as ethers, nitriles, and the like.
  • the ionic NCA 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&- 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 protons or protonated Lewis bases or reducible Lewis acids capable of protonating or abstracting a moiety, such as an alkyl or aryl, from the pre-catalyst after alkylation.
  • the activating cation ( **- ⁇ ), ⁇ + may be a Bronsted acid, capable of donating a proton to the alkylated 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; oxomiuns from ethers, such as dimethyl ether, diethyl ether, tetrahydrofuran
  • the activating cation (L**-H) d + may also be a moiety, such as silver, tropylium, carbeniums, ferroceniums, and mixtures; preferably carboniums and ferroceniums; most preferably triphenyl carbonium.
  • each Q is a fluorinated hydrocarbyl having 1-20 carbon atoms, more preferably each Q is a fluorinated aryl group, and most preferably each Q is a pentafluoryl aryl group.
  • suitable ⁇ ⁇ also include diboron compounds as disclosed in U.S. Patent No. 5,447,895, which is fully incorporated herein by reference.
  • the ionic NCA activator is N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-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 tetra(perfluorophenyl)borate.
  • the catalyst precursors employed in the present process can also be activated with cocatalysts or activators that comprise non-coordinating anions containing metalloid-free cyclopentadienide ions. These are described in U.S. Patent Publication 2002/0058765 Al, published on 16 May 2002, and for the instant invention, require the addition of a co-activator to the catalyst pre-cursor.
  • the present process 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 alkylated transition metal compounds. The alkylated transition metal compound is formed from the reaction of the catalyst pre-cursor and the co-activator.
  • tris(pentafluorophenyl) boron or aluminum act to abstract a hydrocarbyl ligand to yield an invention cationic transition metal complex and stabilizing noncoordinating anion, see EP 0427697 A and EP 0520732 A for illustrations of analogous group 4 metallocene compounds. Also, see the methods and compounds of EP 0495375 A.
  • zwitterionic complexes using analogous Group 4 compounds see U.S. Patent Nos.5,624,878; 5,486,632; and 5,527,929.
  • the catalyst-precursor-to-activator molar ratio may be any ratio.
  • Combinations of the described activator compounds may also be used for activation.
  • the pre-catalyst (all pre-catalysts)-to-activator molar ratio is from 1:10 to 1:1; 1:10 to 10:1; 1:10 to 2:1; 1:10 to 3:1; 1:10 to 5:1; 1:2 to 1.2:1; 1:2 to 10:1; 1:2 to 2:1; 1:2 to 3:1; 1:2 to 5:1; 1:3 to 1.2:1; 1:3 to 10:1; 1:3 to 2:1; 1:3 to 3:1; 1:3 to 5:1; 1:5 to 1:1; 1:5 to 10:1; 1:5 to 2:1; 1:5 to 3:1; 1:5 to 5:1; 1:1 to 1:1.2.
  • the pre-catalyst-to- co-activator molar ratio is from 1:100 to 100:1; 1:75 to 75:1; 1:50 to 50:1; 1:25 to 25:1; 1:15 to 15:1; 1:10 to 10:1; 1:5 to 5:1, 1:2 to 2:1; 1:100 to 1:1; 1:75 to 1:1; 1:50 to 1:1; 1:25 to 1:1; 1:15 to 1:1; 1:10 to 1:1; 1:5 to 1:1; 1:2 to 1:1; 1:10 to 2:1.
  • Preferred activators and activator/co-activator combinations include methylalumoxane, modified methylalumoxane, mixtures of methylalumoxane with dimethylanilinium tetrakis(pentafluorophenyl)borate or tris(pentafluorophenyl)boron, and mixtures of trimethyl aluminum or triethyl aluminum or triisobutyl aluminum or tri-n-octylaluminum with dimethylanilinium tetrakis(pentafluorophenyl)borate or tris(pentafluorophenyl)boron or dimethylanilinium tetrakis(perfluoronaphthyl)borate.
  • activator/co- activator combinations include tri-n-octylaluminum with dimethylanilinium tetrakis(pentafluorophenyl)borate, tri-n-octylaluminum with dimethylanilinium tetrakis(perfluoronaphthyl)borate, and methylalumoxane with dimethylanilinium tetrakis(pentafluorophenyl)borate.
  • scavenging compounds are used with NCA activators.
  • Typical aluminum or boron alkyl components useful as scavengers are represented by the general formula X JZ2 where J is aluminum or boron, R x is a ⁇ ⁇ 2 ⁇ alkyl radical, for example, methyl, ethyl, propyl, butyl, pentyl, isomers thereof, and each Z is independently R x or a different univalent anionic ligand, such as halogen (CI, Br, I), alkoxide (OR x ), and the like.
  • Most preferred aluminum alkyls include triethylaluminum, diethylaluminum chloride, tn-iso- butylaluminum, tri-w-octylaluminum. tri-w-hexylaluminum, trimethylaluminum, and the like.
  • Preferred boron alkyls include triethylboron. Scavenging compounds may also be alumoxanes and modified alumoxanes including methylalumoxane and modified methylalumoxane.
  • the catalyst system useful in the present invention may further comprise a support material.
  • a support material supports, methods of supporting, modifying, and activating supports for single-site catalyst, such as metallocenes, is discussed in, for example, METALLOCENE-BASED POLYOLEFINS, Vol. 1, pp. 173-218 (J. Scheirs & W. Kaminsky eds., John Wiley & Sons, 2000).
  • Desirable carriers are inorganic oxides that include Group 2, 3, 4, 5, 13, and 14 oxides and chlorides in one embodiment, and more particularly, inorganic oxides and chlorides of Group 13 and 14 atoms.
  • support materials include silica, alumina, silica-alumina, magnesium chloride, graphite, and mixtures thereof.
  • useful supports include magnesia, titania, zirconia, montmorillonite (EP 0 511 665 Bl), phyllosilicate, and the like. Also, combinations of these support materials may be used, for example, silica- chromium, silica-alumina, silica-titania, and the like. Additional support materials may include those porous acrylic polymers described in EP 0 767 184 B l.
  • the two catalyst components reside on a single support particle.
  • each catalyst can be supported on different support particles.
  • the in-reactor blends described herein are used as the styrenic modifiers of linear ethylene containing polymers and are blended with at least one linear ethylene polymer to prepare the compositions of this invention.
  • the blend composition possesses a unique combination of strong shear thinning, good melt strength (elasticity) and strong mechanical properties, such as elongation and tensile strength.
  • ⁇ polymers that have long chain branches exhibit a plateau in the function of ⁇ ( ⁇ ), whereas linear polymers do not have such a plateau.
  • the plateau in the aforementioned plot will shift to lower phase angles ⁇ when the amount of long chain branching occurring in the polymer sample increases.
  • SAOS small amplitude oscillatory shear
  • the sum of the %'s is equal to the zero shear viscosity, ⁇ 0 .
  • An indication of high levels of branched structure is a high value of ⁇ 5 , corresponding to the relaxation time of 100 s, relative to the zero shear viscosity.
  • the viscosity fraction of the 100 s relaxation time is r
  • Shear thinning is characterized by the decrease of complex viscosity with increasing frequency, and is described below.
  • the resistance of a polymer melt to flow (steady-state viscosity) along a cylindrical tube decreases with increasing flow or shear rate. This is commonly referred to as shear thinning.
  • the viscosity is generally constant at low shear rates. This is the Newtonian region and the viscosity there is called the zero shear viscosity. It is commonly more difficult to reach the Newtonian region in very polydisperse commercial polymers.
  • the viscosity drops inversely with a power of the shear rate. This is called the power law region.
  • the crossover from the Newtonian behavior to the power law behavior is characterized by a critical shear rate, usually defined for convenience as the shear rate at which the viscosity has decreased to 20% below the zero shear viscosity. Shear thinning is believed to result from the stretching of the "entangled" state to an "oriented” state of the polymer chains when the applied shear rate is higher than this critical shear rate.
  • the product of this critical shear rate and the characteristic relaxation time of the polymer is a constant. This relationship appears to be quite universal for entangled polymers (linear or branched, monodisperse or polydisperse, and melts or solution) although a rather limited number of commercial polymers were used in the tests.
  • the longer relaxation time for a branched polymer makes the critical shear rate smaller than would be for a linear polymer with the same viscosity.
  • the viscosity of a branched polymer is lower at high shear rates and the curves of viscosity plotted against shear rate for linear and branched polymers may cross.
  • a polymer containing long branched structure(s) exhibits a higher degree of shear thinning than a linear polymer in the molten state.
  • One way to quantify the shear thinning is to use a ratio of the difference between the complex viscosity at a frequency of 0.1 rad/s and the complex viscosity at a frequency of 100 rad/s to the complex viscosity at a frequency of 0.1 rad/s when the complex viscosity is measured at 190°C.
  • This ratio is the typical output of the SAOS experiments.
  • a conventional SAOS test temperature is 190°C.
  • a dynamic mechanical spectrometer such as the Advanced Rheometrics Expansion System (ARES).
  • a high degree of shear thinning indicates a polymer is readily processable in high shear fabrication processes, for example by injection molding.
  • the polystyrene/polyethylene graft copolymer has a degree of shear thinning of 0.95 or more at 190°C (preferably 0.96 or more, 0.97 or more, 0.98 or more, or 0.99 or more).
  • the blend compositions may have tensile strength greater than 15 MPa (as measured by ASTM D 638 at 23°C), preferably greater than 20 MPa, preferably greater than 30 MPa.
  • the blend compositions may have elongation at break greater than 300% (as measured by ASTM D 638 at 23°C), preferably greater than 400%, preferably greater than 500%, preferably greater than 600%, preferably greater than 700%, preferably greater than 800%, preferably greater than 900%.
  • the blend compositions can also have tensile strength at 100% elongation greater than 8 MPa (as measured by ASTM D 638 at 23 °C), preferably greater than 10 MPa, preferably greater than 12 MPa.
  • the blend compositions can have a tensile strength above 8 MPa, preferably a tensile strength above 10 MPa, and/or an elongation at break of at least 600%, preferably at least 700%, preferably at least 800%, and preferably at least 900%.
  • the blend compositions also show strain hardening in tensile measurements. After the yield point, the blend undergoes a period of strain hardening, in which the stress increases again with increasing strain up to the ultimate strength in a stress-strain curve as measured according to ASTM D 638 at 23 °C.
  • the blend compositions can also have a toughness (as measured by ASTM D 638 at
  • Toughness is defined as the ability of polymer to absorb applied energy up to break. With respect to a plot of stress versus strain, the area under the stress-strain curve is used as a measure of the toughness at room temperature.
  • the blend compositions can have a density (as measured by ASTM 1505) in a range of from 0.840 g/cm 3 to 0.940 g/cm 3 in one embodiment, from 0.850 g/cm 3 to 0.93 g/cm 3 in a more particular embodiment, from 0.850 g/cm 3 to 0.920 g/cm 3 in yet a more particular embodiment, from 0.860 g/cm 3 to 0.930 g/cm 3 in yet a more particular embodiment, from 0.870 g/cm 3 to 0.92 g/cm 3 in yet a more particular embodiment, less than 0.925 g/cm 3 in yet a more particular embodiment, less than 0.920 g/cm 3 in yet a more particular embodiment, and less than 0.900 g/cm 3 in yet a more particular embodiment.
  • a density as measured by ASTM 1505
  • the blend compositions preferably have a bulk density of from 0.400 g/cm 3 to 0.900 g/cm 3 in one embodiment, and from 0.420 g/cm 3 to 0.800 g/cm 3 in another embodiment, and from 0.430 g/cm 3 to 0.500 g/cm 3 in yet another embodiment, and from 0.440 g/cm 3 to 0.60 g/cm 3 in yet another embodiment, wherein a desirable range may comprise any upper bulk density limit with any lower bulk density limit described herein.
  • blend compositions preferably have one or more of the following properties:
  • a Young's Modulus (modified ASTM D 638 at 23 °C) of at least 250 MPa or more (preferably 300 MPa or more, preferably 350 MPa or more);
  • strain at break modified ASTM D 638 at 23 °C of at least 150% or more (preferably 200% or more, preferably 230% or more);
  • toughness (determined as described in the Examples section) of at least 25 MJ/m 3 or more (preferably 30 MJ/m 3 or more, preferably 32 MJ/m 3 or more).
  • the blend composition has one or more of the following properties:
  • phase angle ( ⁇ ) of at least about 2° lower than the linear polyethylene at a complex modulus of 10 kPa at 190°C;
  • the blend composition has a tensile strength of above, equal to or less than about 5 MPa below the tensile strength of the linear polyethylene at room temperature. In any embodiment of this invention, the blend composition has an elongation at break of above, equal to or less than about 50% below the elongation at break of the linear polyethylene at room temperature. In any embodiment of this invention, the blend composition has a gel content of less than about 5 wt% (preferably 0 wt%) after extraction in boiling toluene for about 5 hours. USE OF THE POLYMER BLENDS
  • the blend compositions can be used in many applications where thermoplastics are used.
  • the inventive blends provide high melt strength, ease of processability (shear thinning), and higher application temperatures over a wide range of densities.
  • the blend compositions are useful in such forming operations as film, sheet, pipe and fiber extrusion, and co-extrusion, as well as blow molding, injection molding, and rotary molding.
  • Films include blown or cast films formed by coextrusion or by lamination useful as shrink film, cling film, stretch film, sealing films, oriented films, snack packaging, heavy duty bags, grocery sacks, baked and frozen food packaging, cable and wire sheathing, medical packaging, industrial liners, membranes, etc.
  • Fibers include melt spinning, solution spinning and melt blown fiber operations for use in woven or non-woven form to make filters, diaper fabrics, medical garments, geotextiles, etc.
  • Extruded articles include medical tubing, wire and cable coatings, geomembranes, and pond liners. Molded articles include single and multi-layered constructions in the form of bottles, tanks, large hollow articles, rigid food containers and toys, etc.
  • the blend compositions are useful in making films.
  • the films may be of any desirable thickness or composition, in one embodiment from 1 to 100 microns, and from 2 to 50 microns in a more particular embodiment.
  • the resins used to make the films may be blended with other additives such as pigments, antioxidants, fillers, etc., as is known in the art, as long as they do not interfere with the desired film properties.
  • LLDPE Film blowing is the most widely used extrusion technique in terms of polyethylene production volume.
  • LLDPE's have narrower MWD's but contain no long chain branching (LCB). They have high entanglement densities which enhance film stretchability, leading to a higher resistance to damage by foreign objects to avoid tear and any subsequent down time during the high-speed blowing process.
  • LCB long chain branching
  • the high entanglement density makes LLDPE viscous in the molten state.
  • SCB short chain branching
  • SCB short chain branching
  • LLDPE is more viscous at high shear rates when processed in the extruder and the die than LDPE, which contains a certain amount of LCB.
  • LLDPE's show lower extensional stresses at low strain rates in the molten tube and bubble inflation regions, hence more prone to bubble instability.
  • Another important feature in film blowing is its ability to draw down the film so that its final gauge is much thinner than the die gap. However, this is limited by the strength of the melt in the bubble. In the case of a high nip roll speed, the tensile stress in the bubble will exceed the cohesive strength of the melt, leading to film rupture.
  • the blend compositions can also be used as an impact modifier of polypropylene.
  • TPO thermoplastic polyolefin
  • PP polypropylene
  • the TPO mixture can have about 10% to 30% in weight of the inventive polymer blend.
  • Thermoforming processes also favor the use of the high melt strength or the high melt elasticity of polyolefins.
  • Thermoforming is the process of heating a solid plastic article, mostly in the sheet form, to a temperature where it softens, but does not flow, then reshaping it. This process has a large cost advantage over injection molding because of less expensive mold and lower energy expended. However, caution to avoid the buildup of slack in the heated sheet needs to be exercised in the thermoforming process. It has been found that a polyolefin containing a certain amount of branching can improve its melt strength or elasticity, which in turn improves its sagging resistance.
  • thermoforming process of polyethylene is not as popular as that of polypropylene (PP)
  • adding a polyethylene/polystyrene graft copolymer or a similar copolymer as described herein in PE can improve the melt strength of PE during the thermoforming process.
  • the blend compositions may be used in any known application involving molding or extrusion, including consumer goods, industrial goods, construction materials, packaging materials, and automotive parts.
  • the polyethylene/polystyrene graft copolymer or a similar copolymer composition described herein may be molded into desirable end use articles by any suitable means known in the art, including but not limited to, injection molding, gas-assisted injection molding, extrusion blow molding, injection blow molding, injection stretch blow molding, compression molding, rotational molding, foam molding, thermoforming, sheet extrusion, and profile extrusion.
  • the molding processes are well known to those of ordinary skill in the art. They are particularly useful for making articles by injection molding, blow molding, film blowing, extrusion, thermoforming, gas foaming, elasto-welding, and compression molding techniques.
  • Blow molding is another suitable forming means, which includes injection blow molding, multi-layer blow molding, extrusion blow molding, and stretch blow molding, and is especially suitable for substantially closed or hollow objects, such as, for example, gas tanks and other fluid containers.
  • Blow molding is described in more detail in, for example, CONCISE ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING, pp. 90-92 (Jacqueline I. Kroschwitz, ed., John Wiley & Sons, 1990).
  • profile co-extrusion can be used.
  • the profile co-extrusion process parameters are as above for the blow molding process, except the die temperatures (dual zone top and bottom) range from 150°C to 235°C, the feed blocks are from 90°C to 250°C, and the water cooling tank temperatures are from 10°C to 40°C.
  • Preferred articles made using the polyethylene/polystyrene graft copolymer or a similar copolymer composition or its blend with a polyolefin described herein include cookware, storageware, toys, medical devices, medical containers, healthcare items, sheets, crates, containers, bottles, packaging, wire and cable jacketing, pipes, sporting equipment, chair mats, tubing, profiles, instrumentation sample holders and sample windows, automotive, boat and water craft components, and other such articles.
  • the compositions are suitable for automotive components, such as trim parts, parts for dashboards and instrument panels, mirror housing, body panel, protective side molding, and other interior and external components associated with automobiles, trucks, boats, and other vehicles.
  • the disclosed molded parts may also be fabricated using a co-injection molding process, whereby an injection mold is used to form the part and/or lid and the materials are co- injected into the mold to form separate skins.
  • the part and/or lid can be fabricated using an overmolding process, whereby one of the layers is molded first and the other layers are molded over the previously molded structure.
  • Conventional injection molding and thermal molding may also be utilized.
  • injection molding and blow molding techniques may be combined by injection molding a preform, which is transferred to a blow mold, and inflated to form an outer structure with inner structures or layers blown into the outer structure. The process can be repeated to form as many layers as desired.
  • the molded articles made of the compositions of the present invention are formed by thermoforming, blow molding, injection molding, compression molding, or injection-compression molding.
  • Embodiments of the present invention relate to a film comprising the blend compositions disclosed above.
  • Preferred embodiments have a tensile strength within 5 MPa of the tensile strength of the linear polyethylene.
  • a method for producing an alkene terminated polystyrene comprising:
  • a styrenic block copolymer preferably comprising butadiene blocks (preferably the butadiene block is derived essentially from 1,4-butadiene); preferably one or more of a styrene- butadiene diblock, a styrene-butadiene-styrene triblock, a styrene-butadiene multiblock, a styrene-butadiene star block represented by the formula (SB) n (where S represents a styrenic block, B represents a butadiene block, and n is the number of arms and is an integer from 3 to 20) and blends thereof; more preferably styrene-butadiene-styrene triblock copolymer or blends thereof) and an alkene (preferably ethylene) in the presence of a metathesis catalyst (preferably comprising a Group 6 and/or Group 8 metal, preferably at least one of ruthenium, tungsten
  • the alkene terminated polystyrene has a MWD of about 1.2 or less (preferably, the M w of the alkene terminated polystyrene is within 15% of the M w of a single styrenic block of the styrenic block copolymer).
  • M is a Group 8 metal, preferably Ru or Os, preferably Ru;
  • X and X 1 are, independently, any anionic ligand, preferably a halogen (preferably CI), an alkoxide or a triflate, or X and X 1 may be joined to form a dianionic group and may form single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non- hydrogen atoms;
  • L and L 1 are, independently, a neutral two electron donor, preferably a phosphine, a cyclic alkyl amino carbene, or a N-heterocyclic carbene, L and L 1 may be joined to form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;
  • L and X may be joined to form a multidentate monoanionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;
  • L 1 and X 1 may be joined to form a multidentate monoanionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;
  • R and R 1 are, independently, hydrogen or to C30 substituted or unsubstituted hydrocarbyl (preferably a Q to C30 substituted or unsubstituted alkyl or a substituted or unsubstituted C 4 to C 3() aryl);
  • R 1 and L 1 or X 1 may be joined to form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;
  • R and L or X may be joined to form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms
  • the metathesis catalyst is one or more of: 2,6-diisopropylphenylimidoneophylidene molybdenum(VI) bis(t-butoxide), 2,6-diisopropylphenylimidoneophylidene molybdenum(VI) bis(hexafluoro-t-butoxide), 2,6- diisopropylphenylimido neophylidenemolybdenum(VI) bis(trifluoromethanesulfonate) dimethoxyethane adduct, 2,6-diisopropylphenylimidoneophylidene[racemic- BIPHEN]molybdenum(VI), tricyclohexylphosphine[ 1 ,3 -
  • grafting the vinyl terminated polystyrene to a polyolefin preferably, linear polyethylene
  • a polyolefin/polystyrene graft copolymer composition preferably, by reactive blending in the presence of at least one organic peroxide, preferably dicumyl peroxide; preferably a diblock copolymer of polystyrene and polyolefin is produced in a yield of at least 40 wt%, based on the weight of the polyolefin/polystyrene graft copolymer composition).
  • a polymerization catalyst system preferably comprising at least one metallocene catalyst and an activator; preferably at least one metallocene catalyst and an alumoxane
  • a polymerization catalyst system preferably comprising at least one metallocene catalyst and an activator; preferably at least one metallocene catalyst and an alumoxane
  • polyethylene/polystyrene copolymer has one or more of the following properties:
  • phase angle ( ⁇ ) of less than about 45° at a complex modulus of 10 kPa at 190°C;
  • a polyethylene blend composition comprising:
  • a linear polyethylene having a density of at least 0.910 g/cm 3 , preferably 0.940 g/cm 3 or more (and preferably a CDBI of 60% or more; preferably an LLDPE or an HDPE; preferably having an M w of 50,000 g/mol or more, a g' of 0.95 or more, and an M w /M n of from greater than about 1 to about 10, and comprises from 50 mol% to 100 mol% ethylene and from 0 mol% to 50 mol% of C3 to C40 comonomer; preferably the linear polyethylene is a polymer of an ethylene and at least one alpha-olefin having 5 to 20 carbon atoms, where the linear polyethylene has a melt index (190°C/2.16 kg) of from about 0.1 to 15 dg/min; a CDBI of at least 70%; a density of from about 0.910 to about 0.930 g/cm 3
  • phase angle ( ⁇ ) of at least about 2° lower than the linear polyethylene at a complex modulus of 10 kPa at 190°C;
  • composition of paragraph 9 preferably, the article is a film; preferably having a tensile strength within 5 MPa of the tensile strength of the linear polyethylene).
  • M w Weight-average molecular weight, M w , and molecular weight distribution (MWD), M w /M n , where M n is the number-average molecular weight, of HDPE and the polyethylene/polystyrene graft copolymer (PE-g-PS) were characterized using a High Temperature Size Exclusion Chromatograph (SEC), equipped with a differential refractive index detector (DRI), an online light scattering detector, and a viscometer, relative to a polystyrene standard.
  • SEC High Temperature Size Exclusion Chromatograph
  • DRI differential refractive index detector
  • R. R. Chance an online light scattering detector
  • Solvent for the SEC experiment was prepared by dissolving 6 g of butylated hydroxy toluene as an antioxidant in 4 L 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 the 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 hr.
  • TCB Aldrich reagent grade 1,2,4 trichlorobenzene
  • 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 ranged 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/min, and the DRI was allowed to stabilize for 8-9 hr before injecting the first sample.
  • the LS laser was turned on 1 to 1.5 hr before running samples.
  • the concentration, c, at each point in the chromatogram is calculated from the baseline-subtracted DRI signal, I DRI , using the following equation:
  • K D RJ is a constant determined by calibrating the DRI
  • dn/dc is the same as described below for the LS analysis.
  • Units on parameters throughout this description of the SEC method are such that concentration is expressed in g/cm 3 , molecular weight is expressed in kg/mol, and intrinsic viscosity is expressed in dL/g.
  • the light scattering detector used was a Wyatt Technology High Temperature mini-DAW .
  • the polymer molecular weight, M, at each point in the chromatogram is determined by analyzing the LS output using the Zimm model for static light scattering (M. B. Huglin, LIGHT SCATTERING FROM POLYMER SOLUTIONS, Academic Press, 1971):
  • ⁇ ( ⁇ ) is the measured excess Rayleigh scattering intensity at scattering angle ⁇
  • c is the polymer concentration determined from the DRI analysis
  • A2 is the second virial coefficient
  • ⁇ ( ⁇ ) is the form factor for a monodisperse random coil (described in the above reference), and K 0 is the optical constant for the system:
  • A2 1
  • the molecular weight averages usually defined by considering the discontinuous nature of the distribution in which the macromolecules exist in discrete fractions i containing N j molecules of molecular weight M j .
  • the weight-average molecular weight, M w is defined as the sum of the products of the molecular weight M j of each fraction multiplied by its weight fraction w;:
  • weight fraction Wj is defined as the weight of molecules of molecular weight M j divided by the total weight of all the molecules present:
  • the number-average molecular weight, M n is defined as the sum of the products of the molecular weight M j of each fraction multiplied by its mole fraction x j :
  • the ratio of M w /M n is the molecular weight distribution (MWD).
  • n s The specific viscosity, n s , for the solution flowing through the viscometer was calculated from their outputs.
  • M v is the viscosity- average molecular weight based on molecular weights determined by the LS analysis:
  • M v differs ordinarily only slightly from the M w .
  • a WATERS 150C GPC using THF as the permeation solvent at 40°C and equipped with UV and DRI detectors was used to determine the values of M n and M w of SBS and
  • composition and the microstructure of each of these polymers were obtained by !fi NMR using either a VARIAN or BRUKER NMR operating at 500 MHz with deuterated chloroform as the solvent.
  • PE its blend with PE-g-PS, and other polymers were compression-molded into plaques with a thickness of about 0.7 mm and a thickness of about 2 mm using a press at 180°C, a molding time of 15 min, and a press force of 25 tons.
  • Tensile parameters such as the Young's modulus (E 0 ; obtained from the initial slope of the stress-strain curve), the yield strain (e y ), the yield stress (o y ), the modulus at 100% strain (E 10 o) > me strain at break (e3 ⁇ 4), the tensile strength ( ⁇ 3 ⁇ 4), and the tensile toughness (U; calculated as the total area under the stress-strain curve) were then determined.
  • Some of the PE materials described in this invention showed two yield points. According to N. W. Brooks, et ah, J. Macromol. Sci., B 34, 29, 1995, the first yield point corresponds to reorientation/rotation of the lamellae within the spherulites in PE.
  • the reoriented lamellae are oriented at about 45° to the draw direction.
  • the second yield point corresponds to the destruction of the lamellae laying 45° to the draw direction.
  • the subsequent permanent deformation corresponds to a crystallographic slip processes correspond to the breakup of lamellar structures for the lamellae oriented perpendicular to the draw direction, and chain pull-out (along lamellar axes) for those lamellae oriented parallel to the draw direction. Both processes lead to extended chain crystals.
  • the original lamellae are destroyed and then re- crystallize into extended chain crystals, which appear as additional transitions in the stress- strain curve.
  • the values of e y and o y shown in the various tables of this invention were based on the first yield point starting from the lower-strain region of the stress-strain curve.
  • a sample with a dimension of - 23 mm x 6.42 mm was die- cut from the compression-molded plaque with a thickness of about 0.7 mm. It was conditioned under ambient conditions for 24 hr before the DMTA measurement.
  • the instrument used was the DMTA V in tension mode (0.05% strain, 1 Hz frequency, 2°C/min heating rate, and a temperature range of ca. -100 to 150°C).
  • the a and ⁇ relaxation temperatures were determined from the loss tangent maxima.
  • ⁇ listed in the various tables of this invention are those at a complex modulus, G*, of 10 kPa.
  • G* complex modulus
  • the dependence of complex viscosity as a function of frequency can also be determined from the rheological measurements. The following ratio:
  • ⁇ *(0.1 rds) and ⁇ *(100 rds) are the complex viscosities at frequencies of 0.1 and 100 rds, respectively, measured at 190°C and rds is rads or radians. The higher this ratio, the higher is the degree of shear thinning.
  • MI Melt index
  • the crystallization temperature T c and melting temperature T m of the polymer were measured using a DSC Q100 equipped with 50 auto-samplers from TA Instruments. This DSC was calibrated with an indium standard weekly. Typically, 6-10 mg of a polymer was sealed in an aluminum pan with a hermetic lid and loaded into the instrument. In a nitrogen environment, the sample was first cooled to -90°C at 20°C/min. It was heated to 220°C at 10°C/min and melting data (first heat) were acquired. This provides information on the melting behavior under as-received conditions, which can be influenced by thermal history as well as sample preparation method. The sample was then equilibrated at 220°C to erase its thermal history.
  • Crystallization data (first cool) were acquired by cooling the sample from the melt to -90°C at 10°C/min and equilibrated at -90°C. Finally it was heated again to 220°C at 10°C/min to acquire additional melting data (second heat).
  • the exothermic crystallization transition (first cool) was analyzed for peak temperature as T c .
  • the endothermic melting transition (second heat) was analyzed for peak temperature as T m .
  • the styrenic block copolymer was VECTORTM 6241 A, a SBS triblock copolymer, commercially obtained from Dexco Polymers (Houston, TX).
  • Cyclic alkyl amino carbene (CAAC) catalyst D was prepared following the procedure described in WO2011/056884, and Zhan Catalyst 1-B was commercially obtained from Strem Chemicals, Inc. (Newburyport, MA).
  • the HDPE, HD 6706.17 was commercially obtained from ExxonMobil Chemical Company. It had a M n of 22,000, an M w of 76,000, and a branching index, g', is reported to be 0.967. MI was 6.7 dg/min, density was 0.952 g/cm 3 , DSC T c was 114°C, DSC T m was 131°C, and DSC heat of fusion was 188 J/g.
  • DCP Dicumyl peroxide
  • EXCEEDTM PE 2018 (mLLDPE containing 6 wt% hexene) was obtained commercially from ExxonMobil Chemical Company and some of its properties are reported in Table 1, below. From DSC, its T c was 106°C, T m was 119°C, and heat of fusion was 142 J/g.
  • the SBS (VECTOR 6241A) was dissolved in toluene at a concentration of about 8 wt%. The solution was treated over 4A molecular sieves. The dissolved polymer was then precipitated in a large volume of methanol and washed several times by methanol. It was dried in a vacuum oven (50°C for 2 days and then at room temperature for 4 days or longer). Inside a dry box, fresh toluene (dried by alumina beads calcined at 300°C) was used to dissolve the purified SBS to prepare a 10 wt% polymer solution.
  • the metathesis reaction was carried out at an ethylene pressure of 140 psi to 150 psi and a temperature of 40°C for 3 hr.
  • a few drops of ethyl vinyl ether were added to deactivate the catalyst at the end of the reaction.
  • the reaction mixture was precipitated in a large volume of methanol and the resulting polymer was washed several times by methanol. It was then dried in a vacuum oven at room temperature for one week or longer.
  • the polymer was studied by GPC and proton NMR.
  • VTPS-1 and VTPS-2 the VTPS polymers produced by Catalyst D and the Zhan Catalyst 1-B are denoted by VTPS-1 and VTPS-2, respectively.
  • M n and M w of a single PS block in the precursor SBS are 12 and 14 kg/mol, respectively. Therefore, the M n and M w of each VTPS are very close to those of the single PS block in the starting SBS, indicating depolymerization occurred quantitatively to the PS block after the metathesis reaction.
  • the GPC curves in Figure 1 also demonstrate the conversion of the higher molecular weight SBS to the lower molecular weight polymer.
  • the MWD of each VTPS is narrow with a value of 1.1. Consistently NMR data also suggest that the complete polybutadiene middle block of the original SBS was largely degraded except for some minute amounts of vinyl and internal unsaturations left.
  • the VTPS can be used as a macromonomer, which can be homopolymerized or copolymerized with other comonomers.
  • the metathesis and the polymerization reactions can be performed in one pot (the "in-reactor blend” approach), especially in the case of metallocene polymerization, because activator, such as alumoxane or modified alumoxane, is able to deactivate the ruthenium catalyst.
  • Figure 2 is a 2-dimensional HSQC NMR spectrum of the olefinic region from VTPS-2. This plot has the !fi chemical shift horizontally and the 13 C chemical shift vertically shows directly bonded hydrogen/carbon connectivity. The 1 -dimensional spectrum is shown at the top of the figure.
  • vinyl groups When vinyl groups are present the two carbons in the structure have chemical shifts at 114 ppm to 115 ppm and 139 ppm to 140 ppm and the corresponding directly bonded hydrogen shifts are at 4.9 ppm to 5.1 ppm and 5.6 ppm to 5.8 ppm. These intensities at these intersecting areas are labeled in the figure. Their presence demonstrates that vinyl groups have been generated in the reaction product. The other intensities in the data are from additional unsaturated species, most likely internal olefins.
  • SBS SBS
  • VECTOR 6241A SBS
  • the solution was dried over the 4A molecular sieves.
  • the dissolved polymer was then precipitated in a large volume of methanol and washed several times using methanol.
  • the precipitate was dried in a vacuum oven (50°C for 2 days and room temperature for 4 days or longer).
  • Ethenolysis of this larger amount of purified SBS was carried out in a 2-L reactor.
  • the typical reactor drying cycle was performed and it was allowed to cool under nitrogen.
  • About 80 g (approximately 850 mmol butadiene units) of small pieces of SBS were added to the reactor.
  • the reactor containing the polymer was degassed with five high pressure/vent cycles.
  • About 1300 mL of purified toluene was added to the reactor, which was heated to 110°C to dissolve the SBS.
  • the mixture of SBS and toluene was stirred after heated for 15 min. This heating/stirring process was continued for a total of 30 min. Then the reactor was cooled to 40°C.
  • the reactor was pressurized to 140 psi (0.965 MPa) of ethylene.
  • a catalyst solution prepared from 20-mL dichloromethane and 1.24 g (1.69 mmol) Zhan Catalyst IB was added to the SBS solution.
  • the ethylene pressure was maintained and the mixture was stirred at 40°C for 4 h.
  • the reaction was quenched by adding ethyl vinyl ether (2.44 g, 33.8 mmol) dissolved in toluene.
  • the reaction mixture was cooled to 20°C and stirred for 20 min.
  • the reactor was vented and dropped.
  • the dark brown solution was poured slowly into a large body of stirring methanol.
  • the isolated solid VTPS-3 polymer was washed thoroughly with a large amount of methanol and then dried in the hood, then further dried in a vacuum oven.
  • VTPS-3 has a GPC M n of 9,630 g/mol and a GPC M w of 11,100 g/mol.
  • the NMR mole ratio of styrene to vinyl is 111 to 1.
  • HDPE pellets (HD 6709.17, 37.4 g), VTPS-3 (6.6 g), and DCP (0.1 g) were weighed and put inside a plastic bottle. These ingredients were dry mixed by shaking the bottle vigorously for 5 minutes. A BRABENDERTM mixer (50-g capacity) was then heated to 175°C. The dry mix was introduced by a fast rate (completed in less than 0.5 min) into the preheated BRABENDERTM mixer. A rotor speed of 50 rpm was used throughout the run and the system was kept at temperature desired and stable. Mixing was continued for 10 minutes once all the blend components were incorporated in the HDPE. Finally the blend was discharged from the mixer and allowed to cool down. This BRABENDERTM reactive blend was denoted by PE-g-PS (polyethylene/polystyrene graft copolymer).
  • PE-g-PS polyethylene/polystyrene graft copolymer
  • the BRABENDERTM reactive blend of PE-g-PS was cut into small pieces, with a sample weight of about 0.5 g.
  • the cut sample was put inside a pre-weighed stainless steel thimble.
  • Solvent extraction using a soxhlet apparatus refluxing at the boiling point of cyclohexane (80°C) was carried out for 5 hr.
  • the soluble fraction was determined to be 2.8 wt%, suggesting that almost all the VTPS-3 had been grafted to the HDPE in the PE-g-PS, because boiling cyclohexane should be a good solvent for homopolystyrene but not for HDPE.
  • the styrene content in PE-g-PS is about 15 wt% based on the amounts of HDPE and VTPS-3 charged to the BRABENDERTM mixer.
  • Results of the High Temperature Size Exclusion Chromatograph (SEC) are shown in Table 3, below.
  • the SEC trace of PE-g-PS was broad but remained quite unimodal with a low molecular weight shoulder.
  • the gel content of PE-g-PS was determined by solvent extraction using a soxhlet apparatus and refluxing at the boiling point (110°C) of toluene for 5 hours. The insoluble fraction was 0.96 wt%, suggesting that PE-g-PS is almost free of gel.
  • Table 4 compares the properties of PE-g-PS to the neat HDPE.
  • Figure 3 compares the van Gurp-Palmen plot of PE-g-PS compared to the neat HDPE.
  • Figure 4 compares the flow curves of PE-g-PS to HDPE.
  • the grafting reaction of VTPS-3 to HDPE produces a large enhancement in the degree of shear thinning of HDPE, see also the column labeled as "Degree of Shear Thinning" in Table 4.
  • a BRABENDERTM mixer (50g capacity) was heated to 200°C.
  • a rotor speed of 50 rpm was used throughout the run and the system was kept at 200°C. Mixing was continued for 10 min once all the blend components were incorporated in the mLLDPE. Finally the blend was discharged from the mixer and allowed to cool down. This Brabender blend is denoted as "EXCEEDTM + PE-g-PS".
  • An anionic polymerized PS was prepared as follows. Styrene (Sigma Aldrich) was dried over a slurry of finely ground calcium hydride, and vacuum distilled to a storage flask protected from outside air and moisture by a septum. A 1L round bottom flask reactor equipped with a septum and a stir bar was purged thoroughly with nitrogen. A 50mL syringe was purged with nitrogen and was used to uptake 130 mL of anhydrous cyclohexane (Sigma- Aldrich). This cyclohexane was injected through the septum of the reactor. A 3 OmL syringe was purged with nitrogen and was uptake to draw 20 mL of purified styrene from the storage flask of the distilling apparatus. It was then injected into the reactor through the septum.
  • Styrene Sigma Aldrich
  • the content of the reactor was titrated with about 0.1-0.2 mL of sBuLi (sec -butyl lithium, 1.4 M in cyclohexane from Sigma-Aldrich) until a pale yellow color was observed to persist in the solution. Then lmL of sBuLi was charged to the reactor and the color of the solution turned bright orange. The same bright orange color continued for the next 4 hr. About 20 mL of methanol (Sigma-Aldrich) was injected in a small round bottom flask equipped with a stir bar and a septum. The flask was dipped into liquid nitrogen to freeze the content, which was then degassed by drawing vacuum to a needle going through the septum.
  • sBuLi sec -butyl lithium, 1.4 M in cyclohexane from Sigma-Aldrich
  • the procedure was repeated twice. About several drops of this well-degassed methanol was injected into the reactor to terminate the reaction. The polymer solution was then coagulated by a large volume of rapidly stirred methanol. The isolated polymer was washed again with a sufficient amount of methanol. It was first dried in the hood followed by in a vacuum oven. The resulting polymer has a GPC M n of 16,600, a GPC M w of 29,400, and DSC T g of 85°C.
  • a BRABENDERTM mixer (50-g capacity) was heated to 200°C.
  • a rotor speed of 50 rpm was used throughout the run and the system was kept at temperature desired and stable. Mixing was continued for 10 min once all the blend components were incorporated in the mLLDPE. Finally the blend was discharged from the mixer and allowed to cool down. This Brabender blend is denoted as "EXCEEDTM + HDPE/PS".
  • Table 4A shows the EXCEEDTM PE 2018 blend properties compared to the neat EXCEEDTM PE 2018 polymer.
  • Ten wt% of PE-g-PS lowered the phase angle of EXCEEDTM PE 2018; see also Figures 3 and 5.
  • a lower phase angle at a given G* means a higher melt elasticity.
  • 10 wt% of this PE-g-PS in EXCEEDTM PE 2018 enhanced the degree of shear thinning of the host EXCEEDTM PE 2018; see also Figures 4 and 6.
  • 10 wt% of HDPE/PS in EXCEEDTM PE 2018 produced insignificant changes in the phase angle and degree of shear thinning of EXCEEDTM PE 2018; see Table 4 and Figures 3-6.
  • Table 4A Properties of EXCEEDTM PE 2018 Mixed with 10 Wt% of PE-g-PS or HDPE/PS
  • EXCEEDTM PE 2018 blend properties compared to the neat EXCEEDTM PE 2018 polymer are also shown in Table 4.
  • 10 wt% of the inventive PE-g-PS maintains the tensile properties of EXCEEDTM PE 2018; see also Figure 7.
  • HDPE/PS produces a greater drop in tensile strength and elongation at break relative to the neat EXCEEDTM PE 2018 polymer; see also Figure 8.
  • EXCEEDTM Polyethylene 1018 (“EXCEEDTM PE 1018”), an mLLDPE available from ExxonMobil Chemical Company (Houston, Texas), has an MI of 1.0 dg/min, a density of 0.918 g/cm 3 , and a DSC T c of 105°C, a DSC T m of 118°C, and DSC heat of fusion of 122 J/g.
  • PE-g-PS in Example 3 or similar copolymers described in the embodiments of the present invention will also improve the melt strength and shear thinning of this linear ethylene containing polymer in applications, such as blown film, cast film, sheet, pipe and fiber extrusion and co-extrusion as well as blow molding, injection molding and rotary molding.
  • compositions encompasses the terms “consisting essentially of,” “is,” and “consisting of and anyplace “comprising” is used “consisting essentially of,” “is,” or “consisting of may be substituted therefor.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Cette invention porte sur des procédés pour la production d'un polystyrène à terminaison alcène, comprenant : la mise en contact d'un copolymère séquencé styrénique et d'un alcène en présence d'un catalyseur de métathèse dans des conditions suffisantes pour produire un polystyrène à terminaison alcène ayant une fonctionnalité d'insaturation d'au moins 0,7 et une dispersité de masse moléculaire (MWD) inférieure ou égale à 1,5. L'invention porte également sur des procédés pour la production de polymères fonctionnalisés et sur une composition de mélange de polyéthylènes comprenant ces polymères fonctionnalisés.
PCT/US2013/029036 2012-04-18 2013-03-05 Compositions de polyoléfine et leurs procédés de production Ceased WO2013158225A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US13/449,939 US8809456B2 (en) 2012-04-18 2012-04-18 Polyolefin compositions and methods of production thereof
US13/449,939 2012-04-18
EP12168606.7 2012-05-21
EP12168606 2012-05-21

Publications (1)

Publication Number Publication Date
WO2013158225A1 true WO2013158225A1 (fr) 2013-10-24

Family

ID=47913581

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2013/029036 Ceased WO2013158225A1 (fr) 2012-04-18 2013-03-05 Compositions de polyoléfine et leurs procédés de production

Country Status (1)

Country Link
WO (1) WO2013158225A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2982709A1 (fr) * 2014-08-07 2016-02-10 Telene SAS Composition durcissable et article moulé comprenant la composition
CN109503954A (zh) * 2018-10-25 2019-03-22 武汉金发科技有限公司 一种聚丙烯复合材料及其制备方法和应用
CN115703854A (zh) * 2021-08-09 2023-02-17 复旦大学 一种增容剂及其在制备聚烯烃/多糖聚合物复合材料中的应用
CN119490701A (zh) * 2023-08-15 2025-02-21 中国石油化工股份有限公司 一种聚苯乙烯原位增强1,2-聚丁二烯橡胶的制备方法及产物和应用
CN119775497A (zh) * 2023-10-08 2025-04-08 中国石油化工股份有限公司 一种用于乙烯聚合及原位接枝的负载化茂金属催化剂及其制备方法和应用

Citations (55)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4665208A (en) 1985-07-11 1987-05-12 Exxon Chemical Patents Inc. Process for the preparation of alumoxanes
US4716197A (en) * 1986-04-21 1987-12-29 The Dow Chemical Company Polyethylene/EPDM-graft polystyrene blends
EP0277004A1 (fr) 1987-01-30 1988-08-03 Exxon Chemical Patents Inc. Catalyseurs, méthode de préparation de ces catalyseurs et procédé d'utilisation
EP0277003A1 (fr) 1987-01-30 1988-08-03 Exxon Chemical Patents Inc. Catalyseurs, méthode de préparation de ces catalyseurs, et procédé de polymérisation en utilisant ces catalyseurs
EP0279586A2 (fr) 1987-02-14 1988-08-24 Mitsui Petrochemical Industries, Ltd. Aluminoxane finement divisé, son procédé de fabrication et son utilisation
US4874734A (en) 1987-04-03 1989-10-17 Mitsui Petrochemical Industries, Ltd. Process for producing solid catalyst for polymerization of olefins
US4908463A (en) 1988-12-05 1990-03-13 Ethyl Corporation Aluminoxane process
US4924018A (en) 1989-06-26 1990-05-08 Ethyl Corporation Alkylaluminoxane process
US4968827A (en) 1989-06-06 1990-11-06 Ethyl Corporation Alkylaluminoxane process
EP0427697A2 (fr) 1989-10-10 1991-05-15 Fina Technology, Inc. Catalyseurs métallocènes avec acides de Lewis et alkyl-aluminiums
US5026798A (en) 1989-09-13 1991-06-25 Exxon Chemical Patents Inc. Process for producing crystalline poly-α-olefins with a monocyclopentadienyl transition metal catalyst system
US5041584A (en) 1988-12-02 1991-08-20 Texas Alkyls, Inc. Modified methylaluminoxane
US5066741A (en) 1990-03-22 1991-11-19 The Dow Chemical Company Process for preparation of syndiotactic vinyl aromatic polymers
US5091352A (en) 1988-09-14 1992-02-25 Mitsui Petrochemical Industries, Ltd. Olefin polymerization catalyst component, olefin polymerization catalyst and process for the polymerization of olefins
US5103031A (en) 1989-02-21 1992-04-07 Ethyl Corporation Falling film aluminoxane process
EP0495375A2 (fr) 1991-01-16 1992-07-22 The Dow Chemical Company Procédé de préparation de catalyseurs pour polymérisation par addition par oxydation de centres métalliques
US5153157A (en) 1987-01-30 1992-10-06 Exxon Chemical Patents Inc. Catalyst system of enhanced productivity
US5157137A (en) 1991-07-26 1992-10-20 Ethyl Corporation Method of making gel free alkylaluminoxane solutions
EP0520732A1 (fr) 1991-06-24 1992-12-30 The Dow Chemical Company Catalyseur homogène de polymérisation d'olefines obtenu par élimination d'un ligand avec un acide de lewis
WO1993003093A1 (fr) 1991-07-18 1993-02-18 Exxon Chemical Patents Inc. Article thermosoude
US5198401A (en) 1987-01-30 1993-03-30 Exxon Chemical Patents Inc. Ionic metallocene catalyst compositions
US5204419A (en) 1986-11-20 1993-04-20 Mitsui Petrochemical Industries, Ltd. Process for polymerizing olefins
US5206199A (en) 1987-04-20 1993-04-27 Mitsui Petrochemical Industries, Ltd. Catalyst for polymerizing an olefin and process for polymerizing an olefin
US5206197A (en) 1991-03-04 1993-04-27 The Dow Chemical Company Catalyst composition for preparation of syndiotactic vinyl aromatic polymers
US5235081A (en) 1992-03-18 1993-08-10 Ethyl Corporation Method of removing gel forming materials from methylaluminoxanes
US5241025A (en) 1987-01-30 1993-08-31 Exxon Chemical Patents Inc. Catalyst system of enhanced productivity
EP0561476A1 (fr) 1992-03-18 1993-09-22 Akzo Nobel N.V. Solution de polyméthylaluminoxane avec stabilisation améliorée de la solution
US5248801A (en) 1992-08-27 1993-09-28 Ethyl Corporation Preparation of methylaluminoxanes
EP0570982A1 (fr) 1992-05-22 1993-11-24 Tosoh Corporation Catalyseurs et procédé de préparation de polymères d'oléfine
EP0594218A1 (fr) 1986-09-24 1994-04-27 Mitsui Petrochemical Industries, Ltd. Procédé de polymérisation d'oléfines
WO1994010180A1 (fr) 1992-11-02 1994-05-11 Akzo N.V. Aryloxyaluminoxanes
US5384299A (en) 1987-01-30 1995-01-24 Exxon Chemical Patents Inc. Ionic metallocene catalyst compositions
US5391793A (en) 1992-11-02 1995-02-21 Akzo Nobel N.V. Aryloxyaluminoxanes
US5447895A (en) 1994-03-10 1995-09-05 Northwestern University Sterically shielded diboron-containing metallocene olefin polymerization catalysts
US5486632A (en) 1994-06-28 1996-01-23 The Dow Chemical Company Group 4 metal diene complexes and addition polymerization catalysts therefrom
US5502124A (en) 1992-07-01 1996-03-26 Exxon Chemical Patents Inc. Transition metal olefin polymerization processes
US5527929A (en) 1994-08-02 1996-06-18 The Dow Chemical Company Zwitterionic biscyclopentadienyl complexes
US5624878A (en) 1993-06-24 1997-04-29 The Dow Chemical Company Titanium (II) or zirconium (II) complexes and addition polymerization catalysts therefrom
US5703187A (en) 1989-08-31 1997-12-30 The Dow Chemical Company Pseudo-random copolymers formed by use of constrained geometry addition polymerization catalysts
US5747406A (en) 1997-01-10 1998-05-05 Union Carbide Chemicals & Plastics Technology Corporation Catalyst composition for the production of olefin polymers
EP0511665B1 (fr) 1991-05-01 1998-07-22 Mitsubishi Chemical Corporation Catalyseur pour polymérisation d'une oléfine et procédé de production de polymère d'oléfine
EP0500944B1 (fr) 1990-07-24 1998-10-07 Mitsui Chemicals, Inc. Catalyseur pour polymerisation alpha-olefinique et production d'une poly-alpha-olefine a l'aide de ce catalyseur
WO1998043983A1 (fr) 1997-04-03 1998-10-08 Colorado State University Research Foundation Compositions a anions monoheteroborane polyhalogenes
EP0767184B1 (fr) 1995-10-04 1999-08-18 Sumitomo Chemical Company, Limited Support pour catalyseur de polymérisation d'oléfines, catalyseur de polymérisation d'oléfines et procédé de préparation de polymère d'oléfines
US5942459A (en) 1995-02-21 1999-08-24 Mitsubishi Chemical Corporation Catalysts for olefin polymerization and a process for preparing olefin polymers therewith
US6069213A (en) 1997-12-16 2000-05-30 Union Carbide Chemicals & Plastics Technology Corporation Mixed catalyst system
US6245856B1 (en) 1996-12-17 2001-06-12 Exxon Chemical Patents, Inc. Thermoplastic olefin compositions
US6255426B1 (en) 1997-04-01 2001-07-03 Exxon Chemical Patents, Inc. Easy processing linear low density polyethylene
US6268438B1 (en) 1996-12-17 2001-07-31 Exxonmobil Chemical Patents Inc. Thermoplastic elastomeric compositions
US6288171B2 (en) 1998-07-01 2001-09-11 Advanced Elastomer Systems, L.P. Modification of thermoplastic vulcanizates using random propylene copolymers
US20020058765A1 (en) 2000-08-09 2002-05-16 Sigurd Becke Catalyst system for the polymerization of olefins
US20060173123A1 (en) 2002-08-12 2006-08-03 Yang Henry W Modified polyethylene compositions
CN101230119A (zh) * 2008-02-28 2008-07-30 中国科学院化学研究所 一种聚苯乙烯/聚乙烯合金及其专用相容剂与制备方法
WO2011056884A2 (fr) 2009-11-09 2011-05-12 Exxonmobil Chemical Patents Inc. Complexes carbéniques de sels métalliques de lithium et/ou de magnésium et leurs utilisations
WO2011079799A1 (fr) * 2009-12-30 2011-07-07 Zannan Scitech Co., Ltd. Catalyseur de métathèse fortement actif sélectif vis-à-vis de romp et rcm

Patent Citations (58)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4665208A (en) 1985-07-11 1987-05-12 Exxon Chemical Patents Inc. Process for the preparation of alumoxanes
US4716197A (en) * 1986-04-21 1987-12-29 The Dow Chemical Company Polyethylene/EPDM-graft polystyrene blends
EP0594218A1 (fr) 1986-09-24 1994-04-27 Mitsui Petrochemical Industries, Ltd. Procédé de polymérisation d'oléfines
US5204419A (en) 1986-11-20 1993-04-20 Mitsui Petrochemical Industries, Ltd. Process for polymerizing olefins
EP0277004A1 (fr) 1987-01-30 1988-08-03 Exxon Chemical Patents Inc. Catalyseurs, méthode de préparation de ces catalyseurs et procédé d'utilisation
EP0277003A1 (fr) 1987-01-30 1988-08-03 Exxon Chemical Patents Inc. Catalyseurs, méthode de préparation de ces catalyseurs, et procédé de polymérisation en utilisant ces catalyseurs
US5198401A (en) 1987-01-30 1993-03-30 Exxon Chemical Patents Inc. Ionic metallocene catalyst compositions
US5241025A (en) 1987-01-30 1993-08-31 Exxon Chemical Patents Inc. Catalyst system of enhanced productivity
US5153157A (en) 1987-01-30 1992-10-06 Exxon Chemical Patents Inc. Catalyst system of enhanced productivity
US5384299A (en) 1987-01-30 1995-01-24 Exxon Chemical Patents Inc. Ionic metallocene catalyst compositions
US4952540A (en) 1987-02-14 1990-08-28 Mitsui Petrochemical Industries, Ltd. Finely divided aluminoxane, process for producing same and its use
EP0279586A2 (fr) 1987-02-14 1988-08-24 Mitsui Petrochemical Industries, Ltd. Aluminoxane finement divisé, son procédé de fabrication et son utilisation
US4874734A (en) 1987-04-03 1989-10-17 Mitsui Petrochemical Industries, Ltd. Process for producing solid catalyst for polymerization of olefins
US5206199A (en) 1987-04-20 1993-04-27 Mitsui Petrochemical Industries, Ltd. Catalyst for polymerizing an olefin and process for polymerizing an olefin
US5091352A (en) 1988-09-14 1992-02-25 Mitsui Petrochemical Industries, Ltd. Olefin polymerization catalyst component, olefin polymerization catalyst and process for the polymerization of olefins
US5041584A (en) 1988-12-02 1991-08-20 Texas Alkyls, Inc. Modified methylaluminoxane
US4908463A (en) 1988-12-05 1990-03-13 Ethyl Corporation Aluminoxane process
US5103031A (en) 1989-02-21 1992-04-07 Ethyl Corporation Falling film aluminoxane process
US4968827A (en) 1989-06-06 1990-11-06 Ethyl Corporation Alkylaluminoxane process
US4924018A (en) 1989-06-26 1990-05-08 Ethyl Corporation Alkylaluminoxane process
US5703187A (en) 1989-08-31 1997-12-30 The Dow Chemical Company Pseudo-random copolymers formed by use of constrained geometry addition polymerization catalysts
US5026798A (en) 1989-09-13 1991-06-25 Exxon Chemical Patents Inc. Process for producing crystalline poly-α-olefins with a monocyclopentadienyl transition metal catalyst system
EP0427697A2 (fr) 1989-10-10 1991-05-15 Fina Technology, Inc. Catalyseurs métallocènes avec acides de Lewis et alkyl-aluminiums
US5066741A (en) 1990-03-22 1991-11-19 The Dow Chemical Company Process for preparation of syndiotactic vinyl aromatic polymers
EP0500944B1 (fr) 1990-07-24 1998-10-07 Mitsui Chemicals, Inc. Catalyseur pour polymerisation alpha-olefinique et production d'une poly-alpha-olefine a l'aide de ce catalyseur
EP0495375A2 (fr) 1991-01-16 1992-07-22 The Dow Chemical Company Procédé de préparation de catalyseurs pour polymérisation par addition par oxydation de centres métalliques
US5206197A (en) 1991-03-04 1993-04-27 The Dow Chemical Company Catalyst composition for preparation of syndiotactic vinyl aromatic polymers
EP0511665B1 (fr) 1991-05-01 1998-07-22 Mitsubishi Chemical Corporation Catalyseur pour polymérisation d'une oléfine et procédé de production de polymère d'oléfine
EP0520732A1 (fr) 1991-06-24 1992-12-30 The Dow Chemical Company Catalyseur homogène de polymérisation d'olefines obtenu par élimination d'un ligand avec un acide de lewis
WO1993003093A1 (fr) 1991-07-18 1993-02-18 Exxon Chemical Patents Inc. Article thermosoude
US5157137A (en) 1991-07-26 1992-10-20 Ethyl Corporation Method of making gel free alkylaluminoxane solutions
EP0561476A1 (fr) 1992-03-18 1993-09-22 Akzo Nobel N.V. Solution de polyméthylaluminoxane avec stabilisation améliorée de la solution
US5329032A (en) 1992-03-18 1994-07-12 Akzo Chemicals Inc. Polymethylaluminoxane of enhanced solution stability
US5235081A (en) 1992-03-18 1993-08-10 Ethyl Corporation Method of removing gel forming materials from methylaluminoxanes
US5416229A (en) 1992-03-18 1995-05-16 Akzo Nobel Chemicals Inc. Polymethylaluminoxane of enhanced solution stability
EP0570982A1 (fr) 1992-05-22 1993-11-24 Tosoh Corporation Catalyseurs et procédé de préparation de polymères d'oléfine
US5502124A (en) 1992-07-01 1996-03-26 Exxon Chemical Patents Inc. Transition metal olefin polymerization processes
US5248801A (en) 1992-08-27 1993-09-28 Ethyl Corporation Preparation of methylaluminoxanes
WO1994010180A1 (fr) 1992-11-02 1994-05-11 Akzo N.V. Aryloxyaluminoxanes
US5391793A (en) 1992-11-02 1995-02-21 Akzo Nobel N.V. Aryloxyaluminoxanes
US5624878A (en) 1993-06-24 1997-04-29 The Dow Chemical Company Titanium (II) or zirconium (II) complexes and addition polymerization catalysts therefrom
US5447895A (en) 1994-03-10 1995-09-05 Northwestern University Sterically shielded diboron-containing metallocene olefin polymerization catalysts
US5486632A (en) 1994-06-28 1996-01-23 The Dow Chemical Company Group 4 metal diene complexes and addition polymerization catalysts therefrom
US5527929A (en) 1994-08-02 1996-06-18 The Dow Chemical Company Zwitterionic biscyclopentadienyl complexes
US5942459A (en) 1995-02-21 1999-08-24 Mitsubishi Chemical Corporation Catalysts for olefin polymerization and a process for preparing olefin polymers therewith
EP0767184B1 (fr) 1995-10-04 1999-08-18 Sumitomo Chemical Company, Limited Support pour catalyseur de polymérisation d'oléfines, catalyseur de polymérisation d'oléfines et procédé de préparation de polymère d'oléfines
US6245856B1 (en) 1996-12-17 2001-06-12 Exxon Chemical Patents, Inc. Thermoplastic olefin compositions
US6268438B1 (en) 1996-12-17 2001-07-31 Exxonmobil Chemical Patents Inc. Thermoplastic elastomeric compositions
US5747406A (en) 1997-01-10 1998-05-05 Union Carbide Chemicals & Plastics Technology Corporation Catalyst composition for the production of olefin polymers
US6255426B1 (en) 1997-04-01 2001-07-03 Exxon Chemical Patents, Inc. Easy processing linear low density polyethylene
WO1998043983A1 (fr) 1997-04-03 1998-10-08 Colorado State University Research Foundation Compositions a anions monoheteroborane polyhalogenes
US6069213A (en) 1997-12-16 2000-05-30 Union Carbide Chemicals & Plastics Technology Corporation Mixed catalyst system
US6288171B2 (en) 1998-07-01 2001-09-11 Advanced Elastomer Systems, L.P. Modification of thermoplastic vulcanizates using random propylene copolymers
US20020058765A1 (en) 2000-08-09 2002-05-16 Sigurd Becke Catalyst system for the polymerization of olefins
US20060173123A1 (en) 2002-08-12 2006-08-03 Yang Henry W Modified polyethylene compositions
CN101230119A (zh) * 2008-02-28 2008-07-30 中国科学院化学研究所 一种聚苯乙烯/聚乙烯合金及其专用相容剂与制备方法
WO2011056884A2 (fr) 2009-11-09 2011-05-12 Exxonmobil Chemical Patents Inc. Complexes carbéniques de sels métalliques de lithium et/ou de magnésium et leurs utilisations
WO2011079799A1 (fr) * 2009-12-30 2011-07-07 Zannan Scitech Co., Ltd. Catalyseur de métathèse fortement actif sélectif vis-à-vis de romp et rcm

Non-Patent Citations (16)

* Cited by examiner, † Cited by third party
Title
"METALLOCENE-BASED POLYOLEFINS", vol. 1, 2, 2000, JOHN WILEY & SONS
"METALLOCENE-BASED POLYOLEFINS", vol. 1, 2000, JOHN WILEY & SONS, pages: 173 - 218
CHEMICAL AND ENGINEERING NEWS, vol. 63, no. 5, 1985, pages 27
CRAIG S W ET AL: "Highly efficient acyclic diene metastasis depolymerization using a ruthenium catalyst containing a N-heterocyclic carbene ligand", MACROMOLECULES, AMERICAN CHEMICAL SOCIETY, WASHINGTON, DC; US, vol. 34, 6 November 2001 (2001-11-06), pages 7929 - 7931, XP002586803, ISSN: 0024-9297, [retrieved on 20011004], DOI: 10.1021/MA011188P *
DATABASE WPI Week 200903, Derwent World Patents Index; AN 2009-A44065, XP002679248 *
E. Y.-X. CHEN; T. J. MARKS: "Cocatalysts for Metal-Catalyzed Olefin Polymerization: Activators, Activation Processes, and Structure-Activity Relationships", CHEM. REV., vol. 100, 2000, pages 1391 - 1434, XP007920121, DOI: doi:10.1021/cr980462j
G. G. HLATKY, COORDINATION CHEM. REV., vol. 181, 1999, pages 243 - 296
GARCIA-FRANCO ET AL., MACROMOLECULES, vol. 34, no. 10, 2001, pages 3115
JACQUELINE I. KROSCHWITZ,: "CONCISE ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING", 1990, JOHN WILEY & SONS, pages: 90 - 92
M. B. HUGLIN: "LIGHT SCATTERING FROM POLYMER SOLUTIONS", 1971, ACADEMIC PRESS
M. VAN GURP; J. PALMEN, RHEOL. BULL., vol. 67, 1998, pages 5 - 8
METALLOCENE-BASED POLYOLEFINS, vol. 1, 2000, pages 261 - 377
N. W. BROOKS ET AL., J. MACROMOL. SCI., vol. 34, 1995, pages 29
R.B. BIRD; R.C. ARMSTRONG; O. HASSAGER: "Dynamics of Polymeric Liquids", vol. 1, 1987, JOHN WILEY AND SONS, pages: 273 - 275
RHEOMETRIC SCIENTIFICTM ARES ANALYZER, 1998
T. SUN; P. BRANT; R. R. CHANCE; W. W. GRAESSLEY, MACROMOLECULES, vol. 34, no. 19, 2001, pages 6812 - 6820

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2982709A1 (fr) * 2014-08-07 2016-02-10 Telene SAS Composition durcissable et article moulé comprenant la composition
WO2016020261A1 (fr) 2014-08-07 2016-02-11 Telene Sas Composition durcissable et article moulé comprenant la composition
CN107109034A (zh) * 2014-08-07 2017-08-29 特伦尼有限公司 可固化组合物和包含所述组合物的模制品
US10017615B2 (en) 2014-08-07 2018-07-10 Telene Sas Curable composition and molded article comprising the composition
CN107109034B (zh) * 2014-08-07 2019-02-19 特伦尼有限公司 可固化组合物和包含所述组合物的模制品
CN109503954A (zh) * 2018-10-25 2019-03-22 武汉金发科技有限公司 一种聚丙烯复合材料及其制备方法和应用
CN109503954B (zh) * 2018-10-25 2021-07-30 武汉金发科技有限公司 一种聚丙烯复合材料及其制备方法和应用
CN115703854A (zh) * 2021-08-09 2023-02-17 复旦大学 一种增容剂及其在制备聚烯烃/多糖聚合物复合材料中的应用
CN115703854B (zh) * 2021-08-09 2024-04-02 复旦大学 一种增容剂及其在制备聚烯烃/多糖聚合物复合材料中的应用
CN119490701A (zh) * 2023-08-15 2025-02-21 中国石油化工股份有限公司 一种聚苯乙烯原位增强1,2-聚丁二烯橡胶的制备方法及产物和应用
CN119775497A (zh) * 2023-10-08 2025-04-08 中国石油化工股份有限公司 一种用于乙烯聚合及原位接枝的负载化茂金属催化剂及其制备方法和应用

Similar Documents

Publication Publication Date Title
US8481647B2 (en) Thermoplastic elastomer polyolefin in-reactor blends and molded articles therefrom
JP6689862B2 (ja) レオロジー特性が改善されたポリマー組成物
US9422385B2 (en) Polyethylene copolymers with vinyl terminated macromonomers as comonomers
US20110136982A1 (en) Thermoplastic Polyolefin Blends
WO2019210029A1 (fr) Procédé de fabrication d'activateurs de type anion non coordonnant dans des solvants hydrocarburés aliphatiques et alicycliques
KR101720920B1 (ko) 프로필렌계 수지 조성물
EP3124514B1 (fr) Résine oléfinique, son procédé de production et composition de résine à base de propylène
WO2012112259A2 (fr) Mélanges de polyoléfines thermoplastiques
US20120245310A1 (en) Vinyl Terminated Higher Olefin Copolymers and Methods to Produce Thereof
WO2010075111A2 (fr) Mélanges de polyoléfines élastomères thermoplastiques en réacteur et articles moulés dérivés
US8809456B2 (en) Polyolefin compositions and methods of production thereof
WO2013158225A1 (fr) Compositions de polyoléfine et leurs procédés de production
WO2014120478A1 (fr) Copolymères de polyéthylène ayant des macromonomères à terminaison vinyle comme comonomères
JP7308011B2 (ja) プロピレン系樹脂組成物およびその製造方法、ならびに該プロピレン系樹脂組成物を用いた成形体
JP6624831B2 (ja) オレフィン系樹脂、該樹脂の製造方法、ペレット、熱可塑性エラストマーおよび架橋ゴム
EP3950738A1 (fr) Composition de résine
JP7483392B2 (ja) プロピレン系樹脂組成物
WO2012134717A2 (fr) Polymères d'oléfines supérieures à terminaison vinyle et leurs procédés de production
US20200172715A1 (en) Blends of Cyclic Olefin Copolymers and Films Prepared Therefrom
US12410273B2 (en) Comb-block copolymers and methods thereof
WO2020112553A1 (fr) Mélanges de copolymères d'oléfine cyclique et films préparés à partir de ceux-ci
JP2020023724A (ja) オレフィン系樹脂、該樹脂の製造方法、ペレット、熱可塑性エラストマーおよび架橋ゴム
WO2020112547A1 (fr) Poly(alpha-oléfines) et procédés associés

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13711207

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13711207

Country of ref document: EP

Kind code of ref document: A1