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WO2007136459A1 - Procédé pour produire des polymères avec des propriétés de manipulation améliorées - Google Patents

Procédé pour produire des polymères avec des propriétés de manipulation améliorées Download PDF

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Publication number
WO2007136459A1
WO2007136459A1 PCT/US2007/007998 US2007007998W WO2007136459A1 WO 2007136459 A1 WO2007136459 A1 WO 2007136459A1 US 2007007998 W US2007007998 W US 2007007998W WO 2007136459 A1 WO2007136459 A1 WO 2007136459A1
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WIPO (PCT)
Prior art keywords
polymer
pellets
produce
polymers
propylene
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Ceased
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PCT/US2007/007998
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English (en)
Inventor
Sudhin Datta
Vetkav Rajagopalan Eswaran
Srivatsan Srinivas Iyer
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ExxonMobil Chemical Patents Inc
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ExxonMobil Chemical Patents Inc
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Publication of WO2007136459A1 publication Critical patent/WO2007136459A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene

Definitions

  • the instant disclosure is directed to a process to produce polymer pellets having improved handling properties.
  • this disclosure is directed to a process to produce ethylene-propylene copolymer pellets having improved handling characteristics.
  • pellets are generally supplied as discrete particles, often referred to as pellets, beads, or the like.
  • Polymer pellets may be difficult to process and/or manufacture due to poor handling characteristics.
  • pellets of various polymers tend to agglomerate upon packaging, and/or during other final processing steps. It is very difficult to break these agglomerates back into free-flowing pellets during downstream processing.
  • Various dusting agents such as low density polyethylene and EVA can be used to minimize the extent of agglomeration.
  • addition of dusting agents requires addition of these extraneous materials, which may also impact certain applications of a polymer.
  • certain dusting agents may not be acceptable when the polymers are to be utilized in applications requiring direct food contact.
  • Another tool available for the prevention of agglomerates is to blend a problematic polymer with polymers which do not tend to form agglomerates, to produce blends which remain free flowing.
  • this approach not only adds cost to the product, but may also restrict the range of potential applications for a particular product.
  • a process to produce polymer pellets having improved handling characteristics comprises the steps of: contacting one or more monomers in the presence of a catalyst within a reactor, under suitable polymerization conditions to produce a polymer having a melt flow rate of about 1 to about 500 dg/min at 230 0 C, 2.16 kg; extruding the polymer into an aqueous bath to produce polymer pellets; separating at least a portion of the aqueous bath from the pellets; aging the pellets for a post-spin time of less than or equal to about 10 minutes, to produce a polymer pellet having a Shore A hardness of greater than or equal to 45, wherein the melt flow rate of the polymer is controlled by inclusion of hydrogen gas within the reactor.
  • calcium stearate and/or emulsifiers may be added to the water that is circulated through the pelletizer to assist in the pelletization by keeping the pellets from forming chains or strands.
  • the pelletizer water supply is often cooled which also assists with the pelletization.
  • Figure 1 is a graphical representation of the Shore A hardness of exemplary and comparative polymers verses the post-spin time.
  • suitable polymerization conditions relates to the selection of polymerization conditions and components, which are necessary to obtain the production of a desired polymer in light of process parameters and component properties.
  • polymerization processes to produce the polymers disclosed herein, as well as numerous variations in the polymerization components available to produce such polymers having one or more of the desired attributes.
  • the term "reactor” is defined to include any container(s) in which a chemical reaction occurs.
  • the term polymer may refer to a homopolymer, a copolymer, an interpolymer, a terpolymer, or the like.
  • a polymer is referred to as comprising a monomer, the monomer is present in the polymer in the polymerized form of the monomer, or in a derivative form of the monomer.
  • alkyl refers to a hydrocarbon group having from 1 to 20 carbon atoms, which may be derived from the corresponding alkane, alkene, or alkyne, by removing one or more hydrogens from the formula. Examples include a methyl group (CH 3 ), which is derived from methane (CH 4 ), and an ethyl group (CH 3 CH 2 ), which is derived from ethane (CH 3 CH 3 ).
  • aryl refers to a hydrocarbon group comprising 5 to 20 carbon atoms that form a conjugated ring structure characteristic of aromatic compounds.
  • aryl groups or substituents include benzene, naphthalene, phenanthrene, anthracene, and the like, which possess alternating double bonding ("unsaturation") within a cyclic structure.
  • An aryl group is derived from an aromatic compound by dropping one or more hydrogens from the formula.
  • substituted alkyl group(s) refers to replacement of at least one hydrogen atom on an alkyl, alkene, alkyne, or aryl group having 1 to 20 carbon atoms, by at least one substituent.
  • substituents include halogen (chlorine, bromine, fluorine, or iodine), amino, nitro, sulfoxy (sulfonate or alkyl sulfonate), thiol, alkylthiol, hydroxy, alkoxy, and straight, branched, or cyclic alkyls, alkenes, or alkynes having 1 to 20 carbon atoms.
  • alkyl substituents include methyl, ethyl, propyl, tert-butyl, isopropyl, isobutyl, and the like.
  • alkoxy substituents include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, secondary butoxy, tertiary butoxy, pentyloxy, isopentyloxy, hexyloxy, heptryloxy, octyloxy, nonyloxy, and decyloxy.
  • haloalkyl refers to straight or branched chain alkyl groups having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted by at least one halogen.
  • stable pellets refers to pellets that do not exhibit tendencies to agglomerate or otherwise render their physical shape unsuitable for down stream processing. Stable pellets maintain a free flowing form, and can be handled in typical bulk-handling equipment.
  • the chromium catalyst may be one of the well-known Phillips catalysts or either belongs to another classification.
  • a definition of the Phillips catalysts may be found in the chapter “Metal alkyl-free Catalysts” from the book by John Boor Jr., “Ziegler-Natta Catalysts and Polymerizations", p.279-324, Academic Press.
  • Melt flow rate (MFR) is determined consistent with ASTM D1238 at 190°C using a 2.16 kg mass, unless otherwise specified.
  • Polymers are produced by contacting one or more monomers in the presence of a catalyst within a reactor, under suitable polymerization conditions.
  • the polymer produced by any one process will have various properties.
  • the polymer is then extruded, which includes the polymer being pelletized (e.g., chopped), or otherwise converted into particles upon exiting the extruder. Often, the pellets are dispersed into an aqueous bath to both cool the pellets and quench the polymerization reaction.
  • Polymers may also be extruded into a fast-flowing stream of water in an underwater pelletizer wherein the extrudate is cut into pellets of the desired size and shape.
  • calcium stearate and/or emulsifiers may be added to the water that is circulated through the pelletizer to assist in the pelletization by keeping the pellets from forming chains or strands.
  • the pelletizer water supply is often cooled which also assists with the pelletization.
  • the pellets are then "dried", in that at least a portion of the aqueous bath is removed from the pellets. This drying step is typically accomplished utilizing a centrifuge or other similar apparatus (a spin dryer) wherein the aqueous bath is preferably centrifugally separated from the pellets.
  • the pellets may be further processed including being cooled, dried, packaged, and/or the like.
  • the delay between exiting the spin dryer and further processing is referred to herein as the "post-spin time", typically expressed in terms of minutes.
  • post-spin time typically expressed in terms of minutes.
  • various polymers become harder in terms of Shore A hardness with respect to time.
  • Stable pellets preferably have a Shore A hardness of at least 40. Pellets having a Shore A hardness of at least 40 tend to be free flowing, and do not typically form agglomerates or otherwise deform so as not to be processable in bulk handling equipment. However, pellets with a Shore A hardness of less than 40 tend to be "sticky" in that they readily adhere to various surfaces, and/or to one another, forming agglomerates.
  • Pellets having a Shore A hardness of less than 40 may tend to form a negative angle of repose, and may tend to bridge or otherwise not flow through bulk handling equipment. Pellets having a Shore A hardness of less than 40 may tend to deform under the weight of adjoining pellets in bags and storage containers. Deformed pellets tend to agglomerate into interlocked cakes that are difficult to break apart. [0020]
  • the post-spin time of a process, wherein the polymer pellet produced is allowed to harden to produce a pellet having an acceptable Shore A hardness (i.e., greater than or equal to about 40 Shore A) involves introducing a residence time within a process.
  • the post-spin time of the instant process is preferably minimized to less than about 10 minutes, more preferably less than about 9 minutes, more preferably less than about 8 minutes, more preferably less than about 7 minutes, more preferably less than about 6 minutes, more preferably less than about 5 minutes, more preferably less than about 4 minutes, more preferably less than about3 minutes, more preferably less than about 2 minutes, more preferably less than about 1 minute.
  • the Shore A hardness of a polymer pellet immediately after the post-spin time is preferably greater than about 40, more preferably greater than about 45, more preferably greater than about 50, more preferably greater than about 55, more preferably greater than about 60, more preferably greater than about 65 Shore A.
  • melt flow rate is typically controlled by temperature, referred to herein as "temperature MFR control", wherein the temperature of the polymerization reactor is controlled around various set-points to produce a polymer having a particular range of melt flow rate.
  • melt flow rate may also be controlled by addition of hydrogen to the polymerization reactor, referred to herein as "hydrogen MFR control.” Addition of hydrogen avoids higher molecular weights and thus, results in a higher melt flow rate at lower operating temperatures than can be achieved using temperature MFR control alone.
  • the amount of hydrogen added to the reactor to control the melt flow rate is typically referred to in terms of a weight to weight ratio of hydrogen feed rate to a monomer feed rate.
  • the melt flow rate of the final polymer may be controlled utilizing a hydrogen feed rate to ethylene feed rate on the order of about 1 to 10,000 ppm hydrogen to ethylene.
  • the control of the flow rates of ethylene and /or comonomer(s) is adjusted so as to keep constant the ratio between the concentrations of the various monomers.
  • the polymers include any polymer formed from the polymerization of one or more olefin monomers (e.g., mono-olef ⁇ ns, poly-olefins, alpha-olefms, and the like, comprising 2 to 20 carbon atoms, preferably comprising 2 to 10 carbon atoms) by a high pressure, low pressure, or intermediate pressure process: or by Ziegler-Natta catalysts, chromium catalysts, metallocene catalysts, and/or the like.
  • olefin monomers e.g., mono-olef ⁇ ns, poly-olefins, alpha-olefms, and the like, comprising 2 to 20 carbon atoms, preferably comprising 2 to 10 carbon atoms
  • olefin monomers e.g., mono-olef ⁇ ns, poly-olefins, alpha-olefms, and the like, comprising 2 to 20 carbon atoms, preferably comprising 2 to
  • Exemplary polymers include the family of polyolefin resins, polyesters (such as polyethylene terephthalate, polybutylene terephthalate), polyamides (such as nylons), polycarbonates, styrene-acrylonitrile copolymers, polystyrene, polystyrene derivatives, polyphenylene oxide, polyoxymethylene, and fluorine- containing thermoplastics.
  • the preferred thermoplastic resins are crystallizable polyolefins that are formed by polymerizing C 2 to C 20 olefins such as, but not limited to, ethylene, propylene and C 4 to C 12 ⁇ -olefins, such as 1-butene, 1- hexene, 1-octene, 2-methyl-l-propene, 3-methyl-l-pentene, 4-methyl-l-pentene, 5-methyl-l-hexene, and mixtures thereof.
  • C 2 to C 20 olefins such as, but not limited to, ethylene, propylene and C 4 to C 12 ⁇ -olefins, such as 1-butene, 1- hexene, 1-octene, 2-methyl-l-propene, 3-methyl-l-pentene, 4-methyl-l-pentene, 5-methyl-l-hexene, and mixtures thereof.
  • Copolymers of ethylene and propylene or ethylene or propylene with another ⁇ -olefin such as 1- butene-1; pentene-1,2- methylpentene-l,3-methylbutene-l ; hexene-1 ,3-methylpentene-l,4- methylpentene-l,3,3-dimethylbutene-l; heptene-1; hexene-1; methylhexene-l; dimethylpentene-1 trimethylbutene-1; ethylpentene-1; octene-1; methylpentene-1; dimethy lhexene- 1 ; trimethylpentene- 1 ; ethylhexene- 1 ; methylethylpentene- 1 ; diethylbutene-1; propylpentane-1; decene-1; methylnonene-1 ; nonene-1; dimethyloctene-1; tri
  • the polymer may further comprise one or more additives including a stabilizer, an inhibitor of oxidative, thermal; and/or ultraviolet light degradation; lubricants, mold release agents, colorants including dyes and pigments, fibrous and particulate fillers and reinforcements, nucleating agents, plasticizers, and the like, utilized in quantities known to those skilled in the art.
  • additives including a stabilizer, an inhibitor of oxidative, thermal; and/or ultraviolet light degradation; lubricants, mold release agents, colorants including dyes and pigments, fibrous and particulate fillers and reinforcements, nucleating agents, plasticizers, and the like, utilized in quantities known to those skilled in the art.
  • the polymer comprises a random propylene polymer comprising propylene, and at least one other alpha-olefin.
  • the random propylene polymer is preferably a copolymer of ethylene and propylene, produced using a metallocene catalyst.
  • the ethylene content in preferably in the range of about 4 to 25 % > more preferably 8 to 20 percent by weight.
  • the preferred copolymers also exhibit MFR's in the range of 1 to 500 dg/min at 230 0 C, 2.16 kg, more preferably 5 to 200 dg/min at 230 0 C, 2.16 kg.
  • the polymer is a random copolymer of propylene and at least one comonomer selected from ethylene, C 4 -C n ⁇ -olefins, and combinations thereof.
  • the copolymer includes ethylene-derived units in an amount ranging from a lower limit of 2%, 5%, 6%, 8%, or 10% by weight to an upper limit of 20%, 25%, or 28% by weight.
  • This embodiment will also include propylene-derived units present in the copolymer in an amount ranging from a lower limit of 72%, 75%, or 80% by weight to an upper limit of 98%, 95%, 94%, 92%, or 90% by weight.
  • Comonomer content and sequence distribution of the polymers can be measured by 13 C nuclear magnetic resonance ( 13 C NMR), and such methods are well known to those skilled in the art.
  • the polymer is a random propylene copolymer having a narrow compositional distribution.
  • the polymer is a random propylene copolymer having a narrow compositional distribution and a melting point as determined by DSC of from 1O 0 C to 105 0 C.
  • the copolymer is described as random because for a polymer comprising propylene, comonomer, and optionally diene, the number and distribution of comonomer residues is consistent with the random statistical polymerization of the monomers. In stereoblock structures, the number of block monomer residues of any one kind adjacent to one another is greater than predicted from a statistical distribution in random copolymers with a similar composition.
  • Historical ethylene-propylene copolymers with stereoblock structure have a distribution of ethylene residues consistent with these blocky structures rather than a random statistical distribution of the monomer residues in the polymer.
  • the intramolecular composition distribution (i.e., randomness) of the copolymer may be determined by 13 C TSTMR, which locates the comonomer residues in relation to the neighbouring propylene residues.
  • the intermolecular composition distribution of the copolymer is determined by thermal fractionation in a solvent, by methods known to those skilled in the art.
  • a copolymer is considered to have a narrow compositional distribution if approximately 75% by weight, preferably 85% by weight, of the copolymer is isolated as one or two adjacent, soluble fractions with the balance of the copolymer in immediately preceding or succeeding fractions.
  • Each of these fractions has a composition (wt% comonomer such as ethylene or other ⁇ -olefin) with a difference of no greater than 20% (relative), preferably 10% (relative), of the average weight % comonomer of the copolymer.
  • the crystallinity of the polymers may be expressed in terms of heat of fusion.
  • Embodiments of the instant disclosure include polymers having a heat of fusion, as determined by differential scanning calorimetry (DSC), ranging from a lower limit of 1.0 J/g, or 3.0 J/g, to an upper limit of 50 J/g, or 10 J/g.
  • DSC differential scanning calorimetry
  • the crystallinity of the polymer may also be expressed in terms of crystallinity percent.
  • the thermal energy for the highest order of polypropylene is estimated at 189 J/g. That is, 100% crystallinity is equal to 189 J/g. Therefore, according to the aforementioned heats of fusion, the polymer has a polypropylene crystallinity within the range having an upper limit of 65%, 40%, 30%, 25%, or 20%, and a lower limit of 1%, 3%, 5%, 7%, or 8%.
  • melting point is the highest peak among principal and secondary melting peaks as determined by DSC.
  • the polymer has a single melting point.
  • a sample of the random propylene copolymer will show secondary melting peaks adjacent to the principal peak, which are considered together as a single melting point. The highest of these peaks is considered the melting point.
  • the polymer preferably has a melting point by DSC ranging from an upper limit of 105 0 C, 90 0 C, 80 0 C, or 70 0 C, to a lower limit of 20 0 C, 25°C, 30 0 C, 35 0 C, 40 0 C, or 45°C.
  • the polymers used in the instant disclosure have a weight average molecular weight (Mw) within the range having an upper limit of 5,000,000 g/mol, 1,000,000 g/mol, or 500,000 g/mol, and a lower limit of 10,000 g/mol, 20,000 g/mol, or 80,000 g/mol, and a molecular weight distribution Mw/Mn (MWD), sometimes referred to as a "polydispersity index" (PDI), ranging from a lower limit of 1.5, 1.8, or 2.0 to an upper limit of 40, 20, 10, 5, or 4.5.
  • Mw and MWD as used herein, can be determined by a variety of methods, including those in U.S. Patent No.
  • the polymer has a Mooney viscosity, ML(l+4) @ 125 0 C, of 100 or less, 75 or less, 60 or less, or 30 or less.
  • Mooney viscosity, as used herein, can be measured as ML(l+4) @ 125°C according to ASTM Dl 646, unless otherwise specified.
  • the polymers used in embodiments of the instant disclosure can have a tacticity index (m/r) ranging from a lower limit of 4 or 6 to an upper limit of 8, 10, or 12.
  • the tacticity index expressed herein as "m/r” is determined by 13 C NMR.
  • the tacticity index m/r is calculated as defined in H.N. Cheng, Macromolecules, 17, 1950 (1984).
  • the designation "m” or “r” describes the stereochemistry of pairs of contiguous propylene groups, "m” referring to meso and "r” to racemic.
  • An m/r ratio of 0 to less than 1.0 generally describes a syndiotactic polymer and an m/r ratio of 1.0 an atactic material.
  • an isotactic material theoretically may have a ratio approaching infinity, and many by-product atactic polymers have sufficient isotactic content to result in ratios of greater than 50.
  • the polymer has isotactic stereoregular propylene crystallinity.
  • stereoregular as used herein means that the predominant number, i.e. greater than 80%, of the propylene residues have the same 1,2 insertion, and the stereochemical orientation of the pendant methyl groups are the same, either meso or racemic.
  • the propylene-based polymers can have a triad tacticity of three propylene units, as measured by 13C NMR of 75% or greater, 80% or greater, 82% or greater, 85% or greater, or 90% or greater. Preferred ranges include from about 50 to about 99 %, more preferably from about 60 to about 99%, more preferably from about 75 to about 99% and more preferably from about 80 to about 99%; and in other embodiments from about 60 to about 97%. Triad tacticity is determined by the methods described in U.S. Patent Application Publication 20040236042.
  • the polymer may be produced by any process that provides the desired polymer properties, in heterogeneous polymerization on a support, such as slurry or gas phase polymerization, or in homogeneous conditions in bulk polymerization in a medium comprising largely monomer or in solution with a solvent as diluent for the monomers.
  • continuous polymerization processes are preferred.
  • homogeneous polymers are often preferred in the instant disclosure.
  • the polymerization process is a single stage, steady state, polymerization conducted in a well-mixed continuous feed polymerization reactor.
  • the polymerization can be conducted in solution, although other polymerization procedures such as gas phase or slurry polymerization, which fulfil the requirements of single stage polymerization and continuous feed reactors, are contemplated.
  • the polymer may be made advantageously by the continuous solution polymerization process described in WO 02/34795, advantageously in a single reactor and separated by liquid phase separation from the alkane solvent.
  • Preferred methods for producing the polymers are found in U.S. Patent Application Publication 20040236042 and U.S. Patent 6,881,800, which are incorporated by reference herein.
  • the polymers can include copolymers prepared according the procedures in WO 02/36651 which is incorporated by reference here.
  • the polymer can include polymers consistent with those described in WO 03/040201, WO 03/040202, WO 03/040095, WO 03/040201, WO 03/040233, and/or WO 03/040442.
  • Pyridine amine complexes such as those described in WO03/040201 are also useful to produce the polymers useful herein.
  • the catalyst can involve a fluxional complex, which undergoes periodic intra-molecular re-arrangement so as to provide the desired interruption of stereoregularity as in U.S. 6,559,262.
  • the catalyst can be a stereorigid complex with mixed influence on propylene insertion, see Rieger EP1070087.
  • the catalyst described in EP1614699 could also be used.
  • the process of the instant disclosure provides an inexpensive route to manufacture stable polymeric pellets after a post-spin time of less than or equal to about 10 minutes.
  • the instant process is now exemplified including the use of hydrogen MFR control and comparative temperature MFR control, for the manufacture of polymers with the appropriate MFR and ethylene content, along with free flowing and storage-stable pellet characteristics.
  • Example 1 a copolymer of ethylene and propylene was produced according to the process of the instant disclosure using hydrogen MFR control, wherein the reactor temperature was maintained at 92.5°C.
  • a hafnium- metallocene catalyst was used in conjunction with a fluoro-borate activator.
  • the reactor operating conditions are given in Table Ia.
  • the pellets produced were easily processed and did not exhibit any tendencies to agglomerate.
  • the composition of the product was 14.22 % ethylene and the MFR was 99.14.
  • the hardness of the pellet was measured using a Durometer (Type Shore A). The pellet characteristics are shown below in Table Ib.
  • PostSpinDryMin' refers to the time (measured here in minutes) after the pellet has left the spin dryer. The time of interest is the time lapsed after the pellet has been cut and the cooling process has begun. It is estimated that pellets spend about 5 to 10 seconds in transit from the pelletizer to the spin dryer.
  • Example 2 a copolymer of ethylene and propylene was made utilizing hydrogen MFR control, wherein the reactor temperature was maintained at 92.5 C. A hafhium-metallocene catalyst was used in conjunction with a fluoro- borate activator.
  • Comparative Example 3 the polymer was produced utilizing temperature MFR control. A copolymer of ethylene and propylene was made wherein the reactor temperature was maintained at 92.5 C. A hafhium- metallocene catalyst was used in conjunction with a fluoro-borate activator.
  • the polymer produced had poor handling characteristics and agglomerated upon packaging.
  • Comparative Example 4 was also produced using temperature MFR control.
  • a copolymer of ethylene and propylene was made wherein the reactor temperature was maintained at 105 0 C.
  • a hafnium-metallocene catalyst was used in conjunction with a fluoro-borate activator.
  • the polymer produced had poor handling characteristics and agglomerated upon packaging.
  • Figure 1 is a graphical representation of Shore A hardness vs. post-spin time of Examples 1 and 2 and Comparative Examples 3 and 4.

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Abstract

La présente description concerne un procédé permettant de produire des pastilles polymères ayant des caractéristiques de manipulation améliorées. Le procédé comprend les étapes consistant à mettre en contact un ou plusieurs monomères en présence d'un catalyseur dans un réacteur, dans des conditions de polymérisation appropriées pour produire un polymère ayant un indice de fluidité d'environ 1 à environ 500 dg/min à 230°C, 2,16 kg; extruder le polymère dans un bain aqueux pour produire des pastilles polymères; séparer au moins une partie du bain aqueux des pastilles et, après centrifugation, laisser vieillir les pastilles pendant une durée inférieure ou égale 10 minutes à environ, pour produire une pastille polymère ayant une dureté Shore A supérieure ou égale à 45, l'indice de fluidité du polymère étant contrôlé par l'inclusion de gaz hydrogène dans le réacteur.
PCT/US2007/007998 2006-05-18 2007-03-30 Procédé pour produire des polymères avec des propriétés de manipulation améliorées Ceased WO2007136459A1 (fr)

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WO2013081756A1 (fr) * 2011-12-02 2013-06-06 Exxonmobil Chemical Patents Inc. Compositions de polymères et compositions non tissées préparées à partir de celles-ci

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US20040024146A1 (en) * 2000-10-25 2004-02-05 Friedersdorf Chris B. Processes and apparatus for continuous solution polymerization
WO2006083515A1 (fr) * 2005-01-31 2006-08-10 Exxonmobil Chemical Patents Inc. Melanges polymeres et paillettes et leurs procedes de fabrication
WO2006138052A1 (fr) * 2005-06-13 2006-12-28 Exxonmobil Chemical Patents Inc. Compositions de melange thermoplastique

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Publication number Priority date Publication date Assignee Title
US20040024146A1 (en) * 2000-10-25 2004-02-05 Friedersdorf Chris B. Processes and apparatus for continuous solution polymerization
US20050192416A1 (en) * 2000-10-25 2005-09-01 Friedersdorf Chris B. Processes and apparatus for continuous solution polymerization
WO2006083515A1 (fr) * 2005-01-31 2006-08-10 Exxonmobil Chemical Patents Inc. Melanges polymeres et paillettes et leurs procedes de fabrication
WO2006138052A1 (fr) * 2005-06-13 2006-12-28 Exxonmobil Chemical Patents Inc. Compositions de melange thermoplastique

Cited By (3)

* Cited by examiner, † Cited by third party
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US9279047B2 (en) 2008-09-30 2016-03-08 Exxonmobil Chemical Patents Inc. Polymer compositions and nonwoven compositions prepared therefrom
WO2013081756A1 (fr) * 2011-12-02 2013-06-06 Exxonmobil Chemical Patents Inc. Compositions de polymères et compositions non tissées préparées à partir de celles-ci
US8710148B2 (en) 2011-12-02 2014-04-29 Exxonmobil Chemical Patents Inc. Polymer compositions and nonwoven compositions prepared therefrom

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