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WO2004039852A1 - Copolymere d'ethylene de faible densite, procede de fabrication de celui-ci, et melanges comprenant ledit copolymere - Google Patents

Copolymere d'ethylene de faible densite, procede de fabrication de celui-ci, et melanges comprenant ledit copolymere Download PDF

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WO2004039852A1
WO2004039852A1 PCT/US2003/033765 US0333765W WO2004039852A1 WO 2004039852 A1 WO2004039852 A1 WO 2004039852A1 US 0333765 W US0333765 W US 0333765W WO 2004039852 A1 WO2004039852 A1 WO 2004039852A1
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ethylene copolymer
bis
cyclopentadienyl
pellets
ethylene
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WO2004039852A9 (fr
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Weiguo Hu
Thomas Chen-Chi Yu
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ExxonMobil Chemical Patents Inc
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ExxonMobil Chemical Patents Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers

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  • This invention relates to processes for preparing pelletized low density elastomeric copolymers of ethylene and a higher alpha olefin monomer, and the novel pelletized resins and blends resulting from such processes.
  • the invention provides improved, pelletized, very low density ethylene copolymers and processes for their production.
  • Figure 1 is a Solid State Nuclear Magnetic Resonance (SSNMR) spectrum of a solidified ethylene-octene copolymer made in accordance with the current invention, in comparison to a similar ethylene-octene copolymer made with a mono-cyclopentadienyl catalyst.
  • SSNMR Solid State Nuclear Magnetic Resonance
  • An aspect of this invention provides an ethylene copolymer pellet comprising 55wt% to 85wt% of ethylene derived units and 15wt% to 45wt% of units derived from C 4 to C 8 alpha-olefin, having a density of from 0.85 g/cm 3 to
  • Another aspect of the invention provides an ethylene copolymer pellet comprising 55wt% to 85wt% of ethylene derived units and 15wt% to 45wt% of units derived from C 4 to C 8 alpha-olefin, having a density of from 0.85 g/cm 3 to
  • a melt index of from 0.1 to 50 dg/min, and a monoclinic to orthorhombic crystallite ratio of greater than 0.5 made by the process of polymerizing ethylene and a C 4 to C 8 alpha-olefin with a bis-cyclopentadienyl metallocene in a diluent to form a slurry of molten polymer and diluent, removing at least a portion of the diluent from the slurry, pelletizing the slurry in a pelletizer, and quenching the pellets in a cooling solution.
  • Another aspect of the invention provides a process for copolymerizing ethylene and at least one alpha-olefin comprising selecting a bis-cyclopentadienyl catalyst having a reactivity ratio product (r ⁇ r 2 ) of between 0.1 to 0.8, polymerizing ethylene and a C 4 -C 8 alpha-olefin comonomer with the bis-cyclopentadienyl catalyst, producing a copolymer resin having from 55wt% to 85wt% of ethylene derived units and 15wt% to 45wt% of units derived from the C 4 to C 8 alpha-olefin, the resin having a density in a range of 0.85g/cm 3 to 0.88g/cm 3 and a melt index of from 0.1 to 50 dg/min, forming pellets from the resin, and quenching the pellets in a cooling solution at a rate of greater than about 10°C per minute.
  • This invention is a novel pelletized low-density elastomer comprising a copolymer of ethylene and a C 4 to C 8 alpha-olefin monomer, and a process for making the novel pelletized elastomer.
  • polymerization of the elastomer is conducted in a single continuous solution reactor to generate a random copolymer.
  • the polymerization reactor may be a liquid filled, continuous flow, stirred tank reactor providing full back mixing for random copolymer production.
  • the reactor may be cooled by a reactor jacket or cooling coils, autorefrigeration, prechilled feeds or combinations of all three to absorb the heat of the exothermic polymerization reaction.
  • Autorefrigerated reactor cooling requires the presence of a vapor phase in the reactor.
  • Adiabatic reactors with prechilled feeds in which the polymerization exotherm is absorbed by permitting a temperature rise of the polymerizing liquid may be used. Hydrogen may be used to control molecular weight.
  • the reactor temperature may also be used to influence the molecular weight of the polymer fraction produced.
  • Examples of particular reactor configurations and processes that may be used for making the compositions of the present invention are described in detail in WO 99/45049, PCT/USO 1/32299 filed October 17, 2001, and U.S. Patent No. 6,319,998, the disclosures of which are hereby incorporated herein by reference.
  • the catalysts useful for this invention are cyclopentadienyl metallocene complexes which have two cyclopentadienyl ring systems for ligands, or bis- cyclopentadienyl metallocenes.
  • bis-cyclopentadienyl metallocene and "bis-cyclopentadienyl metallocene catalyst precursor” as used herein shall be understood to refer to compounds possessing a transition metal M, with cyclopentadienyl ligands, at least one non-cyclopentadienyl-derived ligand X, and zero or one heteroatom-containing ligand Y, the ligands being coordinated to M and corresponding in number to the valence thereof.
  • the bis-cyclopentadienyl metallocene catalyst precursors are generally neutral complexes but when activated with a suitable co-catalyst yield an active metallocene catalyst which refers generally to an organometallic complex with a vacant coordination site that can coordinate, insert, and polymerize olefins.
  • the metallocene catalyst precursor is a cyclopentadienyl complex which has two cyclopentadienyl ring systems for ligands.
  • the cyclopentadienyl ligands form a sandwich complex with the metal and can be free to rotate (unbridged) or locked into a rigid configuration through a bridging group.
  • the cyclopentadienyl ring ligands can be like or unlike, unsubstituted, substituted, or a derivative thereof such as a heterocyclic ring system which may be substituted, and the substitutions can be fused to form other saturated or unsaturated rings systems such as tetrahydroindenyl, indenyl, or fluorenyl ring systems.
  • These cyclopentadienyl complexes have the general formula
  • Cp 1 of ligand (Cp ⁇ m ) and Cp 2 of ligand (Cp 2 R 2 p ) are the same or different cyclopentadienyl rings
  • R 1 and R 2 each is, independently, a halogen or a hydrocarbyl, halocarbyl, hydrocarbyl-substituted organometalloid or halocarbyl- substituted organometalloid group containing up to about 20 carbon atoms
  • m is 0 to 5
  • p is 0 to 5
  • two R 1 and/or R 2 substituents on adjacent carbon atoms of the cyclopentadienyl ring associated there with can be joined together to form a ring containing from 4 to about 20 carbon atoms
  • R is a bridging group
  • n is the number of atoms in the direct chain between the two ligands and is 0 to 8, or 0 to 3
  • M is a transition metal having a valence of from 3 to
  • bis-cyclopentadienyl metallocenes of the type described above are the racemic isomers of: ⁇ -(CH 3 ) 2 Si(indenyl) 2 M(Cl) 2 ⁇ -(CH 3 ) 2 Si(indenyl) 2 M(CH 3 ) 2 ⁇ -(CH 3 ) 2 Si(tetrahydroindenyl) 2 M(Cl) 2 ⁇ -(CH 3 ) 2 Si(tetrahydroindenyl) 2 M(CH 3 ) 2 ⁇ -(CH 3 ) 2 Si(indenyl) 2 M(CH 2 CH 3 ) 2 and ⁇ -(C 6 H 5 ) 2 C(indenyl) 2 M(CH 3 ) 2 ; wherein M is chosen from a group consisting of Zr and Hf.
  • Examples of unsymmetrical cyclopentadienyl metallocenes of the type described above are: ⁇ -(C 6 H 5 ) 2 C(cyclopentadienyl)(fluorenyl)M(R) 2 ⁇ -(C 6 H 5 ) 2 C(3-methylcyclopentadienyl)(fluorenyl)M(R) 2 ⁇ -(CH 3 ) 2 C(cyclopentadienyl)(fluorenyl)M(R) 2 ⁇ -(C 6 H 5 ) 2 C(cyclopentadienyl)(2-methylindenyl)M(CH 3 ) 2 ⁇ -(C 6 H 5 ) 2 C(3 -methylcyclopentadienyl)(2-methylindenyl)M(Cl) 2 ⁇ -(C 6 H 5 ) 2 C(cyclopentadienyl)(2,7-dimethylfluorenyl)M(R) 2 and ⁇ -(CH 3
  • the metallocene complexes may be activated with a non-coordinating anion (NCA), described further below.
  • NCA non-coordinating anion
  • a scavenger component such as a trialkyl aluminum scavenger may be added to the reactor feed(s) to prevent deactivation of catalyst by poisons and to increase the apparent activity.
  • noncoordinating anion means an anion which either does not coordinate to the transition metal cation or which is only weakly coordinated to the cation thereby remaining sufficiently labile to be displaced by a neutral Lewis base.
  • “Compatible” noncoordinating anions are those which are not degraded to neutrality when the initially formed complex decomposes. Further, the anion will not transfer an anionic substituent or fragment to the cation so as to cause it to form a neutral four coordinate metallocene compound and a neutral byproduct from the anion.
  • Useful noncoordinating anions are those that are compatible, stabilize the metallocene cation in the sense of balancing its ionic charge in a +1 state, yet retain sufficient lability to permit displacement by an ethylenically or acetylenically unsaturated monomer during polymerization. Additionally, useful anions will be large or bulky in the sense of sufficient molecular size to largely inhibit or prevent neutralization of the metallocene cation by Lewis bases other than the polymerizable monomers that may be present in the polymerization process. Typically the anion will have a molecular size of greater than or equal to about 4 angstroms.
  • NCA's are preferred because of their ability to produce a target molecular weight polymer at a higher temperature than tends to be the case with other activation systems such as alumoxane.
  • Descriptions of ionic catalysts for coordination polymerization using metallocene cations activated by non-coordinating anions appear in the early work in EP-A-0 277 003, EP-A-0 277 004, WO92/00333 and U.S. Patent Nos. 5,198,401 and 5,278,119.
  • Reactive cations other than Bronsted acids capable of ionizing the metallocene compounds include ferrocenium triphenylcarbonium and triethylsilylinium cations.
  • Any metal or metalloid capable of forming a coordination complex which is resistant to degradation by water (or other Bronsted or Lewis Acids) may be used or contained in the anion of the second activator compound.
  • Suitable metals include, but are not limited to, aluminum, gold, platinum and the like.
  • Suitable metalloids include, but are not limited to, boron, phosphorus, silicon and the like. The description of non-coordinating anions and precursors thereto of these documents are hereby incorporated herein by reference.
  • An additional method of making the ionic catalysts uses ionizing anionic pre-cursors which are initially neutral Lewis acids but form the cation and anion upon ionizing reaction with the metallocene compounds, for example tris(pentafluorophenyl) boron acts to abstract an alkyl, hydride or silyl ligand to yield a metallocene cation and stabilizing non-coordinating anion, see EP-A-0 427 697 and EP-A-0 520 732.
  • Ionic catalysts for addition polymerization can also be prepared by oxidation of the metal centers of transition metal compounds by anionic precursors containing metallic oxidizing groups along with the anion groups, see EP-A-0 495 375.
  • non-coordinating anions and precursors thereto of these documents are similarly hereby incorporated herein by reference.
  • activators capable of ionic cationization of the metallocene compounds described herein, and consequent stabilization with a resulting noncoordinating anion include: trialkyl-substituted ammonium salts such as: triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, trimethylammonium tetrakis(p-tolyl)borate, trimethylammonium tetrakis(o-tolyl)borate, tributylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(o,p-dimethylphenyl)borate, tributylammonium tetrakis(m,m
  • N,N-dialkyl anilinium salts such as:
  • N,N-2,4,6-pentamethylanilinium tetraphenylborate dialkyl ammonium salts such as: di-(isopropyl)ammonium tetrakis(pentafluorophenyl)borate, and dicyclohexylammonium tetraphenylborate; and triaryl phosphonium salts such as: triphenylphosphonium tetraphenylborate, tri(methylphenyl)phosphonium tetraphenylborate, and tri(dimethylphenyl)phosphonium tetraphenylborate.
  • suitable anionic precursors include those including a stable carbonium ion, and a compatible non-coordinating anion.
  • tropillium tetrakis(pentafluorophenyl)borate triphenylmethylium tetrakis(pentafluorophenyl)borate, benzene (diazonium) tetrakis(pentafluorophenyl)borate, tropillium phenyltris(pentafluorophenyl)borate, triphenylmethylium phenyl-(trispentafluorophenyl)borate, benzene (diazonium) phenyl-tris(pentafluorophenyl)borate, tropillium tetrakis(2,3,5,6-tetrafluorophenyl)borate, triphenylmemylium tetrakis(2,3,5,6-tetrafluorophenyl)borate, benzene (diazonium) tetrakis(3,4,5-trifluorophenyl)
  • metal ligands include halide moieties, for example, (methyl- phenyl) silylene (tetra-methyl-cyclopentadienyl) (tert-butyl-amido) zirconium dichloride), which are not capable of ionizing abstraction under standard conditions, they can be converted via known alkylation reactions with organometallic compounds such as lithium or aluminum hydrides or alkyls, alkylalumoxanes, Grignard reagents, etc.
  • organometallic compounds such as lithium or aluminum hydrides or alkyls, alkylalumoxanes, Grignard reagents, etc.
  • EP-A-0 500 944, EP-Al-0 570 982 and EP-Al-0 612 768 for processes describing the reaction of alkyl aluminum compounds with dihalide substituted metallocene compounds prior to or with the addition of activating anionic compounds.
  • an aluminum alkyl compound may be mixed with the metallocene prior to its introduction into the reaction vessel. Since the alkyl aluminum is also suitable as a scavenger its use in excess of that normally stoichiometrically required for alkylation of the metallocene will permit its addition to the reaction solvent with the metallocene compound.
  • alumoxane would not be added with the metallocene so as to avoid premature activation, but can be added directly to the reaction vessel in the presence of the polymerizable monomers when serving as both scavenger and alkylating activator.
  • Alumoxanes may also fulfill a scavenging function.
  • Alkylalumoxanes may also be used as catalyst activators, particularly for those metallocenes comprising halide ligands.
  • the alumoxane component useful as catalyst activator typically is an oligomeric aluminum compound represented by the general formula (R-Al-O) ⁇ , which is a cyclic compound, or R(R-A1-
  • R is a C ⁇ to C5 alkyl radical, for example, methyl, ethyl, propyl, butyl or pentyl and "n" is an integer from 1 to about 50. Most preferably, R is methyl and "n" is at least 4, i.e., methylalumoxane (MAO).
  • Alumoxanes can be prepared by various procedures known in the art.
  • an aluminum alkyl may be treated with water dissolved in an inert organic solvent, or it may be contacted with a hydrated salt, such as hydrated copper sulfate suspended in an inert organic solvent, to yield an alumoxane.
  • a hydrated salt such as hydrated copper sulfate suspended in an inert organic solvent
  • Catalyst killer such as water may be added to the effluent of the reactor or reactors, for example at the last stage prior to finishing, so as to prevent additional, difficult to control polymerization during finishing. It is possible that the catalyst is effectively spent at the end of the polymerization; however, the more active bis-cyclopentadienyl catalysts and NCA's have sufficient stability to remain active even after the polymerization proper has ended.
  • the amount of killer and the manner of its addition are tailored to ensure that just enough is added to ensure a complete kill. Excess killer may have to be removed by scavenger or other means such as atomic sieves or other purification columns to ensure that killers are not recycled and act as poisons in the polymerization process.
  • the process also uses a scavenging compound.
  • Trialkyl aluminum may be used as a scavenger, as well as other scavengers known in the art.
  • scavenging compounds as used in this application and in the claims is meant to include those compounds effective for removing polar impurities from the reaction solvent.
  • the bis-cyclopentadienyl metallocene may have at least one cyclopentadienyl ring ligand, or a derivative thereof, having a fused ring, such as a fluorenyl ring system.
  • the bis-cyclopentadienyl metallocene may have hafnium as its transition metal (M).
  • the bis-cyclopentadienyl metallocene described above may be activated with an NCA.
  • the NCA may be tetra-aryl fluorinated and may contain a boron-derived group.
  • the tetra-aryl fluorinated NCA may contain at least two perflourinations, and may have at .least one polycyclic aryl group which may be a fused polycyclic group.
  • the reactor temperature can vary between 0-240°C, or 10-
  • Optimal temperatures can be achieved with progressively increasing polymerization temperature by using a bis-cyclopentadienyl metallocene containing hafnium as the transition metal, especially one having a covalent, single atom bridge coupling the two cyclopentadienyl rings.
  • the reactor may be pressurized up to 120 bar.
  • the process of this invention involves selecting a bis-cyclopentadienyl catalyst system having a product of the reactivity ratio (r ⁇ r ) of less than 1, or within the range of from 0.1 to 0.8, or within the range of from 0.1 to 0.5, to randomly and continuously polymerize ethylene and at least one alpha-olefin to produce an ethylene copolymer having a density of from 0.85 g/cm to 0.88 g/cm .
  • the ethylene copolymer produced by the process of this invention contains about 55 wt% to about 85 wt% ethylene units and from about 15 wt% to about 45 wt% of the C 4 to C 8 alpha-olefin comonomer based upon measurement by C NMR.
  • alpha olefin monomers include, but are not limited to 1-octene, 1- hexene and 1-butene.
  • the product of the reactivity ratio (r ⁇ r ) of the polymerization is a measure of the distribution of comonomer incorporated along the chain.
  • the product of the reactivity ratio, wherein rl is the reactivity ratio of the comonomer (C), and r2 is the reactivity ratio of ethylene (E), can be calculated from the following formula (M. Kakugo et al., Macromolecules, 15, 1150-1152):
  • EE, CC and EC are diad sequence of monomers, which can be expressed in terms of triads as follows:
  • Triads can be determined from the 13 C NMR spectrum using the method described in J Macromol. Set, Rev. Macromol. Chem. Phys., C29, 201-317 by J. C. Randall, incorporated herein by reference.
  • a copolymer with a r ⁇ r 2 greater than 1 is "blocky" and a copolymer with a r ⁇ 2 less than 1 is said to be "alternating.”
  • a regular dispersion of comonomer along the polymer chain can be obtained combined with high comonomer incorporation. Less alpha-olefin needs to be fed to the polymerization reactor and less alpha- olefin needs to be recycled after polymer isolation.
  • the process allows for efficient incorporation of the higher alpha-olefin monomer into the polymer chain, for the production of the novel low density elastomer.
  • efficient incorporation it is meant that there is low incorporation of higher alpha-olefins in diad and triad sequences in the polymer chain, i.e. the process provides for a highly random distribution of the alpha-olefins along the polymer chain.
  • the process of the current invention provides a low density elastomer while incorporating less of the more costly comonomer.
  • the novel low density elastomer also contains a high proportion of monoclinic crystallites.
  • the crystallinity in low density elastomers is low, the mechanical properties of the resin may be influenced by its crystallinity because the modulus of crystalline region is much larger than that of the amorphous region. It is expected that the differences between orthorhombic crystallites and monoclinic crystallites will manifest different mechanical properties in elastomers, for example, a higher proportion of monoclinic crystallites is believed to decrease stickiness when pelletizing the resin for storage and transportation.
  • the ratio of monoclinic to orthorhombic crystallites in an elastomer can be determined by Solid State Nuclear Magnetic Resonance (SSNMR).
  • the resins produced by the inventive process preferably have a ratio of monoclinic crystallites to orthorhombic crystallites (m/o) of greater than 0.5 as calculated by dividing the signal area of the peak at 34.0 ppm (corresponding to monoclinic crystallites) by the signal area of the peak at 33.0 ppm (corresponding to orthorhombic crystallites) in the solid state 13 C NMR spectrum. It is believed that a high MCP/OCP ratio, with a suitable dispersion of short chain branches, can provide benefits in pellet handling and impact performance in an end use blend.
  • the pelletization process can occur, for example, by the direct devolatization process system disclosed in WO02/34795, the disclosure of which is hereby incorporated herein by reference.
  • the m/o ratio may be greater than 1 when the resin is quenched at a rate of greater than about 20°C/minute.
  • the m/o ratio may be greater than 1, or greater than 1.25, when the resin is quenched at a rate of greater than about 20°C/minute.
  • the solvent or diluent is removed from the slurry of molten polymer and diluent by squeezing, evaporating or flashing in the devolatization equipment, and the diluent-free molten polymer is then extruded or pushed through a die plate with a cutting device to produce the dense pellets.
  • diluent-free means that the diluent constitutes less than about 0.5% of the total weight of the slurry.
  • An underwater pelletizer may be used for pelletization.
  • the devolatilized polymer may be advanced to a pelletizer die by a screw.
  • the pelletized die outlet is suitably located underwater.
  • the strands emerging from the die may be cut and the cut pellets slurried in the water diluent.
  • Chilled water is used for pelletizing the resin.
  • the water temperature is selected so that the resin is quenched at a rate of greater than 10°C per minute, or greater than 20°C per minute.
  • Typical dimensions of these pellets range from about 2 mm diameter up to 2 cm diameter and a height or length ranging from about 2 mm to about 2 cm.
  • this invention comprises the novel pelletized elastomeric copolymer of this invention that has been rapidly quenched. It is believed that by rapidly quenching the novel resin of the current invention during pelletization, a higher proportion of the faster forming monoclinic crystallites are generated which solidifies the elastomer pellet surface, which provides reduced stickiness in the pelletized resin and allows the pellets to flow freely.
  • the novel elastomeric copolymer of this invention can be used in blends such as TPO (thermoplastic polyolefin) or TPN (thermoplastic vulcanizate) where the matrix phase surrounds the impact modifier.
  • the elastomer is typically blended with a thermoplastic material having a melting temperature over 120°C.
  • the thermoplastic material may be, for example, polypropylene, such as isotactic polypropylene having a melt flow rate (dg/min) in a range of about 1.5 - 40.
  • the polypropylene may contain minor amounts of ethylene and/or an alpha-olefin of 4-12 carbon atoms ranging from 1 wt% to 40 wt% of the polymer.
  • the blend may comprise about 25 to 97 parts by weight of the thermoplastic material, and about 3 to 75 parts by weight of the elastomeric copolymer of this invention.
  • the pelletized ethylene copolymer of this invention has an MIR value of from 15-40, or from 17-32, or from 20-30, and a molecular weight distribution of from 1.5 to 3 as determined by GPC LALLS.
  • the pelletized ethylene copolymer may have a melt index [MI] within the range of from 0.1 to 50 dg/min, or within the range of from 0.1 to 15 dg/min, or within the range of from 0.1 to 10 dg/min, or within the range of from 0.5 to 5 dg/min.
  • Table 1 provides a list of the test methods employed in the following examples.
  • an ethylene-octene copolymer will be used as example to demonstrate calculation of sequence distribution.
  • One method to describe the molecular features of an ethylene-octene copolymer is sequence distribution of monomers along the polymer molecule.
  • single site catalyst in a single continuous reactor makes copolymer of narrow composition distribution. Therefore, the monomer sequence distribution of the present invention can be determined using spectroscopic analysis.
  • Carbon 13 nuclear magnetic resonance spectroscopy ( C NMR) is highly preferred for this purpose, and is used to establish diad and triad distribution via the integration of spectral peaks.
  • the following polymerization reactions were performed in a stirred, liquid filled 2L jacketed steel reactor equipped to perform continuous insertion polymerization in presence of an inert hydrocarbon (naphtha) solvent at pressures up to 120 bar and temperatures up to 240 °C.
  • the reactor was typically stirred at 1000 rpm during the polymerization.
  • the reaction system was supplied with a thermocouple and a pressure transducer to monitor changes in temperature and pressure continuously, and with means to supply continuously purified ethylene, 1-octene, and solvent.
  • ethylene dissolved in the hydrocarbon solvent, 1-octene, tri-n-octyl aluminum (TO A) used as a scavenger, and optionally H 2 are pumped separately, mixed, and fed to the reactor as a single stream.
  • the stream is refrigerated to below 0 °C.
  • transition metal component (TMC) bis(4-triethylsilylphenyl) methylidene (cyclopentadienyl) (2,7-tertbutyl-fluorenyl) hafnium dimethyl was dissolved in a solvent/toluene mixture (9/1 vol/vol) whereas the ionic precursor of the non-coordinating anion (NCA) activator, which is dimethyl anilinium hydride tetrakis(pentafluorophenyl)boron, was dissolved in toluene/solvent mixture (1/1 vol/vol). Both components were pumped separately, mixed at ambient temperature, and cooled to below about 0 °C prior to entering the reactor.
  • NCA non-coordinating anion
  • the reactor temperature was set by adjusting the temperature of an oil bath used as a reservoir for the oil flowing through the reactor wall jacket to 110 °C.
  • the polymer molecular weight (MW) or MI was controlled independently by adjusting the ethylene conversion in the reactor via the catalyst flow rate.
  • the polymer density was controlled by adjusting the ethylene/1- octene weight ratio in the feed.
  • the reactivity ratio product r (where ri is the reactivity of ethylene and r 2 is the reactivity of octene) can be calculated from the following formulae (M. Kakugo et al., Macromolecules 15, 1150-1152):
  • nr 2 4 (EE)(OO)/(EO) 2 , (1)
  • EE, OO, and EO are diad sequence of monomers, which can be expressed in terms of triad as follows:
  • Table 3 provides a summary of the ethylene-octene copolymers made in accordance with this invention. The comonomer weight percentages are determined by Carbon NMR.
  • Table 4 provides a summary of comparative ethylene-octene copolymers sold under the tradename EngageTM by DupontDow Elastomers, which are believed to be made with mono-cyclopentadienyl catalysts.
  • Table 5 shows a comparison between sample 1, sample 2 and comparative sample 6. The samples were selected for comparison because of the similarities in their melt index (MI) and densities. All test specimens were cut from compression molded 1/8 inch plaque. Test specimens were conditioned according to ASTM D-618 for 40 hours in an ASTM room.
  • MI melt index
  • Samples 1 and 2 have comparable properties to comparative sample 6, and are able to achieve these properties with incorporation of less comonomer. Samples 1 and 2 incorporate 37.4 wt% and 37.3 wt% of octene, respectively, while the control sample incorporates 38.9 wt% of octene. Because one octene is similarly effective in disrupting ethylene crystallinity as do several consecutive octene monomers, the polymer of the present invention achieves comparable mechanical properties by using less octene, which is a more expensive raw material than ethylene.
  • Sample 3 incorporates 36.2 wt% comonomer compared with the Comparative Sample 7, which incorporates 37.7 wt% comonomer. Accordingly, comparable properties are achieved while using less of the more costly octene comonomer.
  • Sample 5 achieves similar physical properties at lower comonomer incorporation, i.e. 36.8 wt% octene of Sample 5 as compared with 38.9 wt% octene of the Comparative Sample 8.
  • Figures la and lb compare the SSNMR results from Sample 2 ( Figure la) with Comparative Sample 6 ( Figure lb).
  • the spectra in Figures la and lb were acquired under the same spectrometer conditions, and the samples were cooled at the same rate.
  • the signal at 32.8 - 33.0 ppm represents the orthorhombic ethylene crystal, while the signal at 34 - 34.2 ppm represents the monoclinic form.
  • the monoclinic to orthorhombic crystallinity ratio in the polymer was established from the NMR measurements by dividing the signal area of the peak at 34.0 ppm (corresponding to monoclinic crystallites) by the signal area of the peak at 33.0 ppm (corresponding to orthorhombic crystallites) in the solid state 13C NMR spectrum.
  • Sample 2 of the current invention made with a bis- cyclopentadienyl catalyst has a higher proportion of monoclinic crystallites than a corresponding resin made with a mono-cyclopentadienyl catalyst.
  • the monoclinic/orthorhombic crystallite ratio (m/o) increases at a higher rate of cooling. Accordingly, the m/o ratio and the beneficial physical properties that arise from an enhanced m/o ratio, for example, decreased stickiness of the pellets, can be controlled using the process of this invention and by controlling the rate of cooling.
  • Ethylene-butene copolymer pellets were made in accordance with the above described invention. Properties of the pellets, which were quenched at a rate of greater than 20°C/minute are provided in Table 9.
  • Escorene AX05B (Impact Polypropylene Copolymer, 35 MFR) CimpactTM is a talc sold by Luzenac America Inc.

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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne de nouveaux granulés d'un copolymère élastomérique de faible densité, un procédé de fabrication desdits granulés, et des mélanges obtenus à partir desdits granulés de copolymère. Les granulés de copolymère élastomérique de l'invention présentent une proportion élevée de cristallites monocliniques.
PCT/US2003/033765 2002-10-28 2003-10-28 Copolymere d'ethylene de faible densite, procede de fabrication de celui-ci, et melanges comprenant ledit copolymere Ceased WO2004039852A1 (fr)

Priority Applications (1)

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AU2003286667A AU2003286667A1 (en) 2002-10-28 2003-10-28 Low density ethylene copolymer, a process for making same and blends comprising such copolymer

Applications Claiming Priority (2)

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US42173502P 2002-10-28 2002-10-28
US60/421,735 2002-10-28

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WO2004039852A1 true WO2004039852A1 (fr) 2004-05-13
WO2004039852A9 WO2004039852A9 (fr) 2004-07-15

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US20090326131A1 (en) * 2008-06-25 2009-12-31 Lg Chem, Ltd. Polypropylene-Based Resin Composition And Automobile Parts Using The Same
US20100087609A1 (en) * 2007-05-09 2010-04-08 Park Dong-Kyu Ethylene alpha-olefin copoymer
US20100273936A1 (en) * 2009-04-28 2010-10-28 Richard Cheng-Ming Yeh Finishing Process for Amorphous Polymers
CN102803374A (zh) * 2010-03-26 2012-11-28 巴塞尔聚烯烃意大利有限责任公司 多相聚烯烃组合物
CN103228721A (zh) * 2010-11-26 2013-07-31 Lg化学株式会社 用于光伏电池模块的封装组合物和包括该封装组合物的光伏电池模块
WO2025114148A1 (fr) * 2023-11-28 2025-06-05 Basell Poliolefine Italia S.R.L. Copolymère d'éthylène et son utilisation dans des compositions de polyoléfines

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WO2000024792A1 (fr) * 1998-10-23 2000-05-04 Exxon Chemical Patents Inc. Procede de copolymerisation olefinique avec des hafnocenes pontes
WO2002034795A1 (fr) * 2000-10-25 2002-05-02 Exxonmobil Chemical Company Inc. Procedes et appareil de polymerisation en solution en continu
US6403737B1 (en) * 1993-05-11 2002-06-11 Basell Technology Company Bv Elastomeric copolymers of ethylene with α-olefins and process for their preparation
US6448341B1 (en) * 1993-01-29 2002-09-10 The Dow Chemical Company Ethylene interpolymer blend compositions

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US6403737B1 (en) * 1993-05-11 2002-06-11 Basell Technology Company Bv Elastomeric copolymers of ethylene with α-olefins and process for their preparation
WO1997026287A1 (fr) * 1996-01-22 1997-07-24 The Dow Chemical Company Polymeres ethyleniques a masse moleculaire ultra-basse
WO2000024792A1 (fr) * 1998-10-23 2000-05-04 Exxon Chemical Patents Inc. Procede de copolymerisation olefinique avec des hafnocenes pontes
WO2002034795A1 (fr) * 2000-10-25 2002-05-02 Exxonmobil Chemical Company Inc. Procedes et appareil de polymerisation en solution en continu

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100087609A1 (en) * 2007-05-09 2010-04-08 Park Dong-Kyu Ethylene alpha-olefin copoymer
US8748547B2 (en) * 2007-05-09 2014-06-10 Lg Chem, Ltd. Ethylene α-olefin copolymer
US8604125B2 (en) * 2008-06-25 2013-12-10 Lg Chem, Ltd. Polypropylene-based resin composition and automobile parts using the same
US9068068B2 (en) 2008-06-25 2015-06-30 Lg Chem, Ltd. Polypropylene-based resin composition and automobile parts using the same
US20090326131A1 (en) * 2008-06-25 2009-12-31 Lg Chem, Ltd. Polypropylene-Based Resin Composition And Automobile Parts Using The Same
US20140066562A1 (en) * 2008-06-25 2014-03-06 Lg Chem, Ltd. Polypropylene-based resin composition and automobile parts using the same
WO2010126720A1 (fr) 2009-04-28 2010-11-04 Exxonmobil Chemical Patents Inc. Copolymères à base d'éthylène, compositions d'huile lubrifiante contenant ceux-ci et leurs procédés de fabrication
US8378042B2 (en) * 2009-04-28 2013-02-19 Exxonmobil Chemical Patents Inc. Finishing process for amorphous polymers
US20100273936A1 (en) * 2009-04-28 2010-10-28 Richard Cheng-Ming Yeh Finishing Process for Amorphous Polymers
CN102803374A (zh) * 2010-03-26 2012-11-28 巴塞尔聚烯烃意大利有限责任公司 多相聚烯烃组合物
CN102803374B (zh) * 2010-03-26 2015-08-19 巴塞尔聚烯烃意大利有限责任公司 多相聚烯烃组合物
CN103228721A (zh) * 2010-11-26 2013-07-31 Lg化学株式会社 用于光伏电池模块的封装组合物和包括该封装组合物的光伏电池模块
US9093585B2 (en) 2010-11-26 2015-07-28 Lg Chem, Ltd. Encapsulation composition for photovoltaic cell module and photovoltaic cell module comprising the same
WO2025114148A1 (fr) * 2023-11-28 2025-06-05 Basell Poliolefine Italia S.R.L. Copolymère d'éthylène et son utilisation dans des compositions de polyoléfines

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