WO2009139851A1 - Compositions de polyoléfine et procédés de traitement de celles-ci à l'aide de sels métalliques - Google Patents

Compositions de polyoléfine et procédés de traitement de celles-ci à l'aide de sels métalliques Download PDF

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WO2009139851A1
WO2009139851A1 PCT/US2009/002934 US2009002934W WO2009139851A1 WO 2009139851 A1 WO2009139851 A1 WO 2009139851A1 US 2009002934 W US2009002934 W US 2009002934W WO 2009139851 A1 WO2009139851 A1 WO 2009139851A1
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lldpe
molecular weight
film
mlldpe
metal salt
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PCT/US2009/002934
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English (en)
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Rainer Kolb
Joel E. Schmieg
Agapios K. Agapiou
David M. Glowczwski
James M. Farley
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Univation Technologies, Llc
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    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • 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
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/06—Metallocene or single site catalysts

Definitions

  • the present invention relates generally to polyolefin compositions and methods of processing the same using processing aids. More specifically, but without limitation, the present invention relates to polyolefin compositions and methods for processing the same using metal salts. Additionally, the invention relates to methods of producing films having an improvement in at least one of reduced melt fracture, head pressure, motor load, increased thermal stability, improved color, and combinations thereof.
  • Linear polyolefins including linear polyethylenes such as linear low density polytethylene (LLDPE), may be difficult to melt process. Specifically, due to a low shear sensitivity when compared to highly branched polyethylenes, the linear polyethylenes can require more extruder power to pump an equivalent amount of polymer melt. As a result, higher extruder head pressures, higher torque, greater motor loads may be required.
  • LLDPE linear low density polytethylene
  • melt fracture also known as “shark skin”
  • can lead to poorer optical properties such as high haze, low gloss, and/or diminished film physical properties that are generally unacceptable.
  • linear polyethylenes such as metallocene linear low density polyethylene (mLLDPE) having a narrow molecular weight distribution
  • mLLDPE metallocene linear low density polyethylene
  • Linear polyethylenes therefore have been the subject of a good deal of effort to eliminate or reduce such problems.
  • the invention provides for a method for processing a linear polyethylene into a film, wherein the method includes contacting a linear low density polyethylene (LLDPE) with a sufficient amount of a carboxylate metal salt to reduce melt fracture and melt processing the LLDPE and the carboxylate metal salt to form the film.
  • LLDPE linear low density polyethylene
  • the LLDPE may have a molecular weight (Mw) from 50,000 g/mol to 180,000 g/mol, a molecular weight distribution from 1.5 to 3.0, and a melt index ratio from 15 to 25.
  • the invention provides a composition including a linear low density polyethylene (LLDPE) and a carboxylate metal salt, wherein the LLDPE may have a molecular weight (Mw) from 50,000 g/mol to 180,000 g/mol, a molecular weight distribution from 1.5 to 3.0, and a melt index ratio from 15 to 25.
  • LLDPE linear low density polyethylene
  • Mw molecular weight
  • the invention provides a method for processing a linear polyethylene into a film, wherein the method includes contacting a linear low density polyethylene (LLDPE) with a sufficient amount of a carboxylate metal salt to improve thermal stability of the polyethylene and melt processing the LLDPE and the carboxylate metal salt to form the film.
  • LLDPE linear low density polyethylene
  • the LLDPE may have a molecular weight (Mw) from 50,000 g/mol to 180,000 g/mol, a molecular weight distribution from between 1.5 to 5.0, and a melt index ratio from 15 to 100.
  • the invention provides a composition including a metallocene catalyzed linear low density polyethylene (mLLDPE) and a carboxylate metal salt, wherein the mLLDPE may have a molecular weight (Mw) of about 50,000 g/mol to about 180,000 g/mol, a molecular weight distribution of between 1.5 and 5.0, and a melt index ratio of between 20 and 100.
  • Mw molecular weight
  • FIG. 1 is a graph comparing the effects of processing aids on film heat seal properties during a first trial.
  • FIG. 2 is a graph comparing the effects of processing aids on film heat seal properties during an alternative trial.
  • FIG. 3 is a graph comparing the effects of processing aids on film hot tack properties during a first trial.
  • FIG. 4 is a graph comparing the effects of processing aids on film hot tack properties during an alternative trial.
  • FIG. 5 is a graph comparing the effects of metal stearates on melt indices of sample resins.
  • FIG. 6 is a graph comparing of the effects of metal stearates on color of sample resins.
  • the invention is directed to polyolefin compositions, for example, a polyethylene composition and methods of processing the polyolefin composition. It is further directed to blown film processes having reduced melt fracture as a result of introducing a processing aid including, but not limited to, a metal stearate to a metallocene catalyzed linear polyethylene (for example, metallocene linear low density polyethylene (mLLDPE)).
  • a processing aid including, but not limited to, a metal stearate to a metallocene catalyzed linear polyethylene (for example, metallocene linear low density polyethylene (mLLDPE)).
  • mLLDPE metallocene linear low density polyethylene
  • LLDPE Linear Low Density Polyethylene
  • the compositions and films are made from a linear low density polyethylene (LLDPE) polymer having a density from about 0.890 g/cm 3 to 0.935 g/cm 3 , from 0.900 g/cm 3 to 0.930 in another embodiment and from 0.910 g/cm 3 to 0.927 in yet another embodiment.
  • LLDPE linear low density polyethylene
  • the LLDPE may have a melt index (MI) or (I 2 ) as measured by ASTM-D-1238-E (190°C, 2.16 kg weight) in the range from 0.01 dg/min to 10 dg/min, from about 0.1 dg/min to 10 dg/min in another embodiment, and from 0.1 dg/min to 5 dg/min in yet another embodiment, and from 0.5 dg/min to 3.5 dg/min in yet another exemplary embodiment.
  • MI melt index
  • I 2 as measured by ASTM-D-1238-E
  • the LLDPE may have a narrow weight average molecular weight to number average molecular weight (Mw/Mn) of greater than 1.5 to less than 5, greater than 2.0 to less than 3.5 in another embodiment and greater than 2.0 to less than 2.5 in yet another embodiment.
  • the polymer blends and films are made from a linear low density polyethylene (LLDPE) polymer having a density of from 0.890 g/cm 3 to 0.940 g/cm 3 and from 0.910 g/cm 3 to 0.935 g/cm 3 in another embodiment.
  • LLDPE linear low density polyethylene
  • the LLDPE may have a melt index (MI) or (I 2 ) as measured by ASTM-D-1238-E (190°C, 2.16 kg weight) in the range from 0.01 dg/min to 10 dg/min, from 0.1 dg/min to 10 dg/min in another embodiment, and from 0.1 dg/min to 5 dg/min in yet another embodiment.
  • MI melt index
  • ASTM-D-1238-E 190°C, 2.16 kg weight
  • the LLDPE may have a weight average molecular weight to number average molecular weight (Mw/Mn) of greater than 1.5 to 5.0.
  • the compositions and films are made from a metallocene linear low density polyethylene (mLLDPE) polymer(s).
  • mLLDPE metallocene linear low density polyethylene
  • linear low density polyethylene polymer or “mLLDPE” polymer refer to a polyethylene copolymer having a density of from 0.940 g/cm 3 or less and from 0.890 to 0.940 g/cm 3 in another embodiment.
  • Polymers having more than two types of monomers, such as, for example, terpolymers, are also included within the term “copolymer” as used herein.
  • the comonomers that are useful in general for making mLLDPE copolymers include alpha-olefins, such as C 3 -C 2 O alpha-olefins and C 3 -Ci 2 alpha-olefins.
  • the alpha-olefin comonomer can be linear or branched, and two or more comonomers can be used, if desired.
  • suitable comonomers include linear C 3 -C] 2 alpha-olefins and alpha- olefins having one or more Ci-C 3 alk yl branches, or an aryl group.
  • Specific examples include propylene; 1-butene; 3-methyl-l-butene; 3,3-dimethyl-l-butene; 1-pentene; 1-pentene with one or more methyl, ethyl or propyl substituents; 4- methyl-1-pentene; 1-hexene with one or more methyl, ethyl or propyl substituents; 1-heptene with one or more methyl, ethyl or propyl substituents; 1-octene with one or more methyl, ethyl or propyl substituents; 1-nonene with one or more methyl, ethyl or propyl substituents; ethyl, methyl or dimethyl-substituted 1- decene; 1-dodecene; and styrene.
  • comonomers in producing mLLDPE may include polar vinyl, conjugated and non-conjugated dienes, acetylene and aldehyde monomers, which can be included in minor amounts in terpolymer compositions.
  • Non-conjugated dienes useful as co-monomers are typically straight chain, hydrocarbon di-olefins or cycloalkenyl-substituted alkenes, having 6 to 15 carbon atoms.
  • Suitable non- conjugated dienes include, for example: (a) straight chain acyclic dienes, such as 1 ,5-hexadiene and 1 ,7-octadiene; (b) branched chain acyclic dienes, such as 5- methyl-l,4-hexadiene; 3,7-dimethyl-l,6-octadiene; and 3,7-dimethyl-l,7- octadiene; (c) single ring alicyclic dienes, such as 1 ,4-cyclohexadiene; 1,5-cyclo- octadiene and 1,7-cyclododecadiene; (d) multi-ring alicyclic fused and bridged ring dienes, such as tetrahydroindene; norbornadiene; methyl-tetrahydroindene; dicyclopentadiene (DCPD); bicyclo-(2.2.1)-hepta-2,5-diene; alkeny
  • the preferred dienes are dicyclopentadiene, 1 ,5-hexadiene, 5-methylene-2- norbornene, 5-ethylidene-2-norbornene, and tetracyclo-(.DELTA.-l l,12)-5,8- dodecene.
  • Particularly preferred diolefins are 5-ethylidene-2-norbornene (ENB), 1 ,5-hexadiene, dicyclopentadiene (DCPD), norbornadiene, and 5-vinyl-2- norbornene (VNB).
  • the amount of comonomer used will depend upon the desired density of the mLLDPE polymer and the specific comonomers selected. One skilled in the art can readily determine the appropriate comonomer content appropriate to produce an mLLDPE polymer having a desired density.
  • the mLLDPE polymer is characterized by having a density of from 0.890 g/cm 3 to 0.935 g/cm 3 , from 0.900 g/cm 3 to 0.930 in another embodiment and from 0.910 g/cm 3 to 0.927 in yet another embodiment.
  • the mLLDPE polymer is characterized by having a melt index (MI) or (I 2 ) as measured by ASTM-D-1238-E (190°C, 2.16 kg weight) in the range from 0.01 dg/min to 10 dg/min, from 0.1 dg/min to 10 dg/min in another embodiment, from 0.1 dg/min to 5 dg/min in yet another embodiment; and from 0.5 dg/min to 3.5 dg/min in another exemplary embodiment.
  • MI melt index
  • I 2 as measured by ASTM-D-1238-E
  • the mLLDPE polymer is characterized by having a narrow weight average molecular weight to number average molecular weight (Mw/Mn) of greater than 1.5 to less than 5, greater than about 2.0 to less than 3.5 in another embodiment and greater than 2.0 to less than 2.5 in yet another embodiment.
  • the mLLDPE polymer is characterized by having a density of from 0.890 g/cm 3 to 0.940 g/cm 3 and from 0.910 g/cm 3 to 0.935 g/cm 3 in another embodiment.
  • the mLLDPE polymer is characterized by having a melt index (MI) or (I 2 ) as measured by ASTM-D-1238-E (190°C, 2.16 kg weight) in the range from 0.01 dg/min to 10 dg/min, from 0.1 dg/min to 10 dg/min in another embodiment and from about 0.1 dg/min to about 5 dg/min in yet another embodiment.
  • MI melt index
  • I 2 190°C, 2.16 kg weight
  • the mLLDPE polymer is characterized by having a weight average molecular weight to number average molecular weight (Mw/Mn) of greater than 1.5 to about
  • LLDPE and mLLDPE polymers of the invention are at times discussed as single polymers, two or more LLDPE or mLLDPE polymers or combinations thereof, having the properties described herein are also contemplated.
  • the mLLDPE polymers described herein may be commercially available under the trade names EXCEEDTM and ENABLETM from ExxonMobil Chemical Co., Houston, TX.
  • metallocene catalyst compounds may contain one or more ligands including cyclopentadienyl (Cp) or cyclopentadienyl-type structures or other similar functioning structure such as pentadiene, cyclooctatetraendiyl and imides. It is understood by one of skill in the art that references made herein to metallocene catalyst compounds and/or systems may also refer to metallocene- type catalyst compounds and/or systems.
  • a catalyst system may be a combination of a catalyst compound and a cocatalyst or activator (described below).
  • Typical metallocene compounds are generally described as containing one or more ligands capable of ⁇ -5 bonding to a transition metal atom, usually, cyclopentadienyl derived ligands or moieties, in combination with a transition metal selected from Group 3 to 8, preferably 4, 5 or 6 or from the lanthanide and actinide series of the Periodic Table of Elements. All reference to the Periodic Table of the Elements herein shall refer to the Periodic Table of the Elements, published and copyrighted by the International Union of Pure and Applied Chemistry, Inc., 2004. Also, any reference to a Group or Groups shall be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC system for numbering groups.
  • EP-A-O 591 756, EP-A-O 520 732, EP-A- 0 420 436, EP-Bl 0 485 822, EP-Bl 0 485 823, EP-A2-0 743 324 and EP-Bl 0 518 092 and PCT publications WO 91/04257, WO 92/00333, WO 93/08221, WO 93/08199, WO 94/01471, WO 96/20233, WO 97/15582, WO 97/19959, WO 97/46567, WO 98/01455, WO 98/06759 and WO 98/011144 describe typical metallocene catalyst compounds and catalyst systems.
  • metallocene catalyst compounds may contain one or more leaving group(s) bonded to the transition metal atom.
  • leaving group may refer to one or more chemical moieties, such as a ligand, bound to the center metal atom of a catalyst component that can be abstracted from the catalyst component by an activator or cocatalyst, thus producing a catalyst species active toward olefin polymerization or oligomerization.
  • reference to "a leaving group” as in a moiety “substituted with a leaving group” includes more than one leaving group, such that the moiety may be substituted with two or more such groups.
  • reference to "a halogen atom” as in a moiety “substituted with a halogen atom” includes more than one halogen atom, such that the moiety may be substituted with two or more halogen atoms, reference to "a substituent” includes one or more substituents, reference to "a ligand” includes one or more ligands, and the like.
  • the Cp ligands are generally represented by one or more bonding systems comprising n bonds that can be open systems or ring systems or fused system(s) or a combination thereof.
  • These ring(s) or ring system(s) are typically composed of atoms selected from Groups 13 to 16 atoms, preferably the atoms are selected from the group consisting of carbon, nitrogen, oxygen, silicon, sulfur, phosphorous, boron and aluminum or a combination thereof.
  • the ring(s) or ring system(s) may be composed of carbon atoms such as, but not limited to, those cyclopentadienyl ligands or cyclopentadienyl-type ligand structures (structures isolobal to cyclopentadienyl).
  • the metal atom may be selected from Groups 3 through 16 and the lanthanide or actinide series of the Periodic Table of Elements, and selected from Groups 4 through 12 in another embodiment, and selected from Groups 4, 5 and 6 in yet a more particular embodiment, and selected from Group 4 atoms in yet another embodiment.
  • metallocene catalyst compounds of the invention are represented by the formula:
  • M is a metal from the Periodic Table of the Elements and may be a Group 3 to 12 atom or a metal from the lanthanide or actinide series Group atom in one embodiment; selected from the group consisting of Sc, Ti, Zr, Hf, V, Nb, Ta, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, and Ni in another embodiment; and selected from the group consisting of Groups 4, 5 or 6 transition metal in yet another embodiment.
  • M is a transition metal from Group 4 such as Ti, Zr or Hf; selected from the group of Zr and Hf in another embodiment; and Zr in yet a more particular embodiment.
  • the oxidation state of M may range from 0 to +7 in one embodiment; and in another embodiment, is +1, +2, +3, +4 or +5; and in yet another illustrative embodiment is +2, +3 or +4.
  • the groups bound to 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 a 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 L A and L B groups of formula (I) are Cp ligands, such as cycloalkadienyl ligands and hetrocylic analogues.
  • the Cp ligands 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 and aluminum and combinations thereof, wherein carbon makes up at least 50% of the ring members.
  • L ⁇ and L B may be any other ligand structure capable of rj -5 bonding to M and alternatively, L A and L B may comprise one or more heteroatoms, for example, nitrogen, silicon, boron, germanium, and phosphorous, in combination with carbon atoms to form a cyclic structure, for example, a heterocyclopentadienyl ancillary ligand.
  • each of L ⁇ and L B may also be other types of ligands including but not limited to amides, phosphides, alkoxides, aryloxides, imides, carbolides, borollides, porphyrins, phthalocyanines, corrins and other polyazomacrocycles.
  • Each L ⁇ and L B may be the same or different type of ligand that is ⁇ -bonded to M.
  • the Cp ligand(s) are 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.
  • illustrative ligands may include cyclopentaphenanthreneyl, benzindenyl,, octahydrofluorenyl, cyclooctatetraenyl, cyclopentacyclododecene, phenanthrindenyl, 3,4-benzofluorenyl, 9- phenylfluorenyl, 8-H-cyclopent[a]acenaphthylenyl, 7-H-dibenzofluorenyl, indeno[l,2-9]anthrene, thiophenoindenyl, thiophenofluorenyl, hydrogenated versions thereof (e.g., 4,5,6,7-tetrahydroindenyl, or "H4Ind”), substituted versions thereof (as described in more detail below), heterocyclic versions thereof and the like, including hydrogenated versions thereof.
  • H4Ind hydrogenated versions thereof
  • Each L A and L B may be unsubstituted or substituted with a combination of substituent R groups.
  • substituent R groups include one or more from the group selected from hydrogen, or linear, branched, alkyl radicals or cyclic alkyl radicals, alkenyl, or aryl radicals or combination thereof, halogens and the like, including all their isomers, for example tertiary butyl, iso-propyl, etc.
  • substituent R groups may comprise 1 to 30 carbon atoms or other substituents having up to 50 non-hydrogen atoms that can each be substituted with halogens or heteroatoms or the like.
  • Alkyl or aryl substituent R groups may include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl groups and the like, including all their isomers, for example, tertiary butyl, isopropyl, and the like.
  • Halogenated hydrocarbyl radicals may include fluoromethyl, fluroethyl, difluroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbyl substituted organometalloid radicals including trimethylsilyl, trimethylgermyl, methyldiethylsilyl and the like; and halocarbyl-substituted organometalloid radicals including tris(trifluoromethyl)-silyl, methyl-bis (difluoromethyl)silyl, bromomethyldimethylgermyl and the like; and disubstitiuted boron radicals including dimethylboron for example; and disubstituted pnictogen or Group 15- containing radicals including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine; and chalcogen or Group 16-containing radicals including methoxy, ethoxy, propoxy, phenoxy
  • Non-hydrogen substituent R groups may include the atoms carbon, silicon, boron, aluminum, nitrogen, phosphorous, oxygen, tin, germanium and the like including olefins such as but not limited to olefinically unsaturated substituents including vinyl-terminated ligands, for example, but-3-enyl, prop-2-enyl, hex-5-enyl, 2- vinyl, or 1-hexene. Also, at least two R groups, preferably two adjacent R groups may be joined to form a ring structure having from 3 to 30 atoms selected from carbon, nitrogen, oxygen, phosphorous, silicon, germanium, boron or a combination thereof. Also, an R group such as 1-butanyl may form a bond to the metal M.
  • the leaving groups Q of formula (I) are monoanionic labile ligands bound to M. Depending on the oxidation state of M, the value for n is 0, 1 or 2 such that formula (I) above represents a neutral metallocene catalyst compound, or a positively charged compound. In a class of embodiments, Q may comprise halogen ions or hydrides.
  • Q may comprise weak bases such as, but not limited to, alkyls, alkoxides, amines, alkylamines, phosphines, alkylphosphines, ethers, carboxylates, dienes, hydrocarbyl radicals having from 1 to 20 carbon atoms, C 6 to Ci 2 aryls, C 7 to C 20 alkylaryls, C 7 to C 20 arylalkyls, hydrides or halogen atoms (e.g., Cl, Br or I) and the like, and combinations thereof.
  • weak bases such as, but not limited to, alkyls, alkoxides, amines, alkylamines, phosphines, alkylphosphines, ethers, carboxylates, dienes, hydrocarbyl radicals having from 1 to 20 carbon atoms, C 6 to Ci 2 aryls, C 7 to C 20 alkylaryls, C 7 to C 20 arylalkyls,
  • Q radicals include those substituents for R as described above and including cyclohexyl, heptyl, tolyl, trifluromethyl, tetramethylene and pentamethylene, methylidene, methyoxy, ethyoxy, propoxy, phenoxy, bis(N-methylanilide), dimethylamide, dimethylphosphide radicals and the like.
  • metallocene catalyst compounds of the invention include those of formula (I) where L A and L B are bridged to each other by a bridging group, A. These bridged compounds are known as bridged, metallocene catalyst compounds represented by the formula (II):
  • L A (A)L B MQ n (II) wherein each L ⁇ and L B are bound to the metal center M, and each Q is bound to the metal center, n being 0 or an integer from 1 to 4, alternatively 1 or 2, and in another embodiment 2; the groups L A , L B M and Q are as defined in formula (I); and the divalent bridging group A is bound to both L A and L B through at least one bond or divalent moiety, each.
  • Non-limiting examples of bridging group A from formula (II) include divalent bridging groups containing at least one Group 13 to 16 atom.
  • bridging group A may be referred to as a divalent moiety such as, but not limited to, carbon, oxygen, nitrogen, silicon, germanium and tin or a combination thereof.
  • bridging group A contains carbon, silicon or germanium atom and in yet another illustrative embodiment, A contains at least one silicon atom or at least one carbon atom.
  • the metallocene catalysts of the invention include their structural or optical or enantiomeric isomers (meso and racemic isomers) and mixtures thereof.
  • the metallocene compounds of the invention may be chiral and/or a bridged metallocene catalyst compound.
  • 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.
  • An activator is defined as any combination of reagents that increases the rate at which a transition metal compound oligomerizes or polymerizes unsaturated monomers, such as olefins.
  • An activator may also affect the molecular weight, degree of branching, comonomer content, or other properties of the oligomer or polymer.
  • the transition metal compounds according to the invention may be activated for oligomerization and/or polymerization catalysis in any manner sufficient to allow coordination or cationic oligomerization and or polymerization.
  • catalysts may contain a formal anionic ligand, such as hydride or hydrocarbyl, with an adjacent (cis) coordination site accessible to an unsaturated monomer. Coordination of an unsaturated monomer to the cis coordination site allows a migratory insertion reaction to form a metal alkyl. Repetition of this process causes the chain growth associated with oligomerization and/or polymerization.
  • An activator is thus any combination of reagents that facilitates formation of a transition metal compound containing cis coordinated olefin and hydride or hydrocarbyl.
  • activation can be achieved by removal of formal anionic or neutral ligand(s), of higher binding affinity than the unsaturated monomer. This removal, also called abstraction, process may have a kinetic rate that is first-order or non-first order with respect to the activator.
  • Activators that remove anionic ligands are termed ionizing activators.
  • activators that remove neutral ligands are termed non-ionizing activators.
  • Activators may be strong Lewis-acids which may play either the role of an ionizing or non-ionizing activator.
  • activation may be a one step or multi step process.
  • One step in this process includes coordinating a hydride or hydrocarbyl group to the metal compound.
  • a separate activation step is removal of anionic or neutral ligands of higher binding affinity than the unsaturated monomer. These activation steps may occur in the presence of an olefin and occur either in series or in parallel. More than one sequence of activation steps is possible to achieve activation.
  • the activator may also act to coordinate a hydride or hydrocarbyl group to the transition metal compound.
  • activation may be effected by substitution of the functional group with a hydride, hydrocarbyl or substituted hydrocarbyl group. This substitution may be effected with appropriate hydride or alkyl reagents of group 1, 2, 12, 13 elements as are known in the art. To achieve activation, it may be necessary to also remove anionic or neutral ligands of higher binding affinity than the unsaturated monomer.
  • Alumoxane and aluminum alkyl activators are capable of alkylation and abstraction activation.
  • Non-limiting examples of preferred Lewis-bases are diethyl ether, dimethyl ether, ethanol, methanol, water, acetonitrile, N,N-dimethylaniline.
  • a ' is an anion, preferably a substituted hydrocarbon, a functional group, or a non-coordinating anion.
  • Non-limiting examples of A " may include halides, carboxylates, phosphates, sulfates, sulfonates, borates, aluminates, alkoxides, thioalkoxides, anionic substituted hydrocarbons, anionic metal complexes and the like.
  • activators include those described in WO 98/07515 such as tris (2,2',2"- nonafluorobiphenyl) fluoroaluminate. Combinations of activators are also contemplated by the invention, for example, alumoxanes and ionizing activators in combinations, see for example, EP-Bl 0 573 120, WO 94/07928 and WO 95/14044 and U.S. Pat. Nos. 5,153,157 and 5,453,410.
  • WO 98/09996 describes activating metallocene catalyst compounds with perchlorates, periodates and iodates including their hydrates.
  • WO 98/30602 and WO 98/30603 describe the use of lithium (2,2'-bisphenyl-ditrimethylsilicate).4THF as an activator for a metallocene catalyst compound.
  • WO 99/18135 describes the use of organo-boron- aluminum activators.
  • EP-Bl-O 781 299 describes using a silylium salt in combination with a non-coordinating compatible anion.
  • WO 2007/024773 suggests the use of activator-supports which may comprise a chemically-treated solid oxide, clay mineral, silicate mineral, or any combination thereof.
  • methods of activation such as using radiation (see EP-Bl-O 615 981), electrochemical oxidation, and the like are also contemplated as activating methods for the purposes of rendering the neutral metallocene catalyst compound or precursor to a metallocene cation capable of polymerizing olefins.
  • Other activators or methods for activating a metallocene catalyst compound are described in, for example, U.S. Pat. Nos. 5,849,852, 5,859,653 and 5,869,723 and PCT WO 98/32775.
  • alumoxanes activators may be utilized as an activator in the catalyst composition of the invention.
  • Alumoxanes are generally oligomeric compounds containing -Al(R)-O-- subunits, where R is an alkyl group.
  • Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane.
  • Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, particularly when the abstractable ligand is a halide.
  • the activator is an alumoxane (modified or unmodified)
  • some embodiments select the maximum amount of activator at a 5000-fold molar excess Al/M over the catalyst precursor (per metal catalytic site).
  • the minimum activator-to-catalyst-precursor is a 1 : 1 molar ratio.
  • Alumoxanes may be produced by the hydrolysis of the respective trialkylaluminum compound.
  • MMAO may be produced by the hydrolysis of trimethylaluminum and a higher trialkylaluminum such as triisobutylaluminum.
  • MMAO's are generally more soluble in aliphatic solvents and more stable during storage.
  • a visually clear methylalumoxane it may be preferable to use a visually clear methylalumoxane.
  • a cloudy or gelled alumoxane can be filtered to produce a clear solution or clear alumoxane can be decanted from the cloudy solution.
  • Another alumoxane is a modified methyl alumoxane (MMAO) cocatalyst type 3 A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A, disclosed in U.S. Pat. No. 5,041,584).
  • MMAO modified methyl alumoxane
  • Aluminum alkyl or organoaluminum compounds which may be utilized as activators (or scavengers) include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and the like.
  • an ionizing or stoichiometric activator such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron, a trisperfluorophenyl boron metalloid precursor or a trisperfluoronaphtyl boron metalloid precursor, polyhalogenated heteroborane anions (see, for example, WO 98/43983), boric acid (see, for example, U.S. Pat. No. 5,942,459) or a combination thereof. It is also within the scope of this invention to use neutral or ionic activators alone or in combination with alumoxane or modified alumoxane activators.
  • Examples of neutral stoichiometric activators may include tri-substituted boron, tellurium, aluminum, gallium and indium or mixtures thereof.
  • the three substituent groups may be each independently selected from the group of alkyls, alkenyls, halogen, substituted alkyls, aryls, arylhalides, alkoxy and halides.
  • the three substituent groups may be independently selected from the group of halogen, mono or multicyclic (including halosubstituted) aryls, alkyls, and alkenyl compounds and mixtures thereof; in a class of embodiments are alkenyl groups having 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms and aryl groups having 3 to 20 carbon atoms (including substituted aryls).
  • the three groups are alkyls having 1 to 4 carbon groups, phenyl, napthyl or mixtures thereof.
  • the three groups are halogenated, fluorinated, aryl groups or mixtures thereof.
  • the neutral stoichiometric activator is trisperfluorophenyl boron or trisperfluoronapthyl boron.
  • Ionic stoichiometric activator compounds may contain an active proton, or some other cation associated with, but not coordinated to, or only loosely coordinated to, the remaining ion of the ionizing compound.
  • Such compounds and the like are described in, for example, European publications EP-A-O 570 982, EP-A-O 520 732, EP-A-O 495 375, EP-Bl-O 500 944, EP-A-O 277 003 and EP-A- 0 277 004, and U.S. Pat. Nos. 5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,384,299 and 5,502,124 and U.S. patent application Ser. No. 08/285,380, filed Aug. 3, 1994.
  • activators may include a cation and an anion component, and may be represented by the following formula:
  • W f+ is a cation component having the charge f+;
  • NCA h' is a non- coordinating anion having the charge h-;
  • f is an integer from 1 to 3;
  • h is an integer from 1 to 3;
  • the cation component, (W f+ ) 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 an analogous metallocene or Group 15 -containing catalyst precursor, resulting in a cationic transition metal species.
  • the activating cation (W f+ ) may be a Bronsted acid, (LB-H f+ ), capable of donating a proton to the transition metal catalytic precursor resulting in a transition metal cation, including ammoniums, oxoniums, phosphoniums, silyliums and mixtures thereof, ammoniums of methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine, triphenylphosphine, and diphenylphosphine, oxoniums from ethers such as dimethyl ether diethyl ether, tetrahydrofuran
  • the activating cation (W + ) may also be an abstracting moiety such as silver, carboniums, tropylium, carbeniums, ferroceniums and mixtures, carboniums and ferroceniums.
  • the activating cation (W f+ ) is triphenyl carbonium or N, N-dimethylanilinium.
  • Each Q is a fluorinated hydrocarbyl group having 1 to 20 carbon atoms, alternatively each Q may be a fluorinated aryl group, and in another embodiment, each Q is a pentafluoryl aryl group.
  • suitable (NCA h ⁇ ) also include diboron compounds as disclosed in U.S. Pat. No. 5,447,895.
  • Additional suitable anions are known in the art and will be suitable for use with the catalysts of the invention. See for example, U.S. Pat. No. 5,278,1 19 and the review articles by S. H. Strauss, "The Search for Larger and More Weakly Coordinating Anions", Chem. Rev., 93, 927 942 (1993) and C. A.
  • boron compounds which may be used as activating cocatalysts in the preparation of the improved catalysts of this invention are tri-substituted ammonium salts such as: trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, tri(t-butyl)ammonium tetraphenylborate, N,N-dimethylanilinium tetraphenylborate, N,N- diethylanilinium tetraphenylborate, N,N-dimethyl-(2,
  • the ionic stoichiometric activator is N 5 N- dimethylanilinium tetra(perfluorophenyl)borate or triphenylcarbenium tetra(perfluorophenyl)borate.
  • NCA non-coordinating anion
  • Non-coordinating anions useful in accordance with this invention are those that are compatible, stabilize the metal cation in balancing its ionic charge, yet retain sufficient lability to permit displacement by an ethylenically or acetylenically unsaturated monomer during polymerization.
  • These types of cocatalysts may use tri-isobutyl aluminum or tri-octyl aluminum as a scavenger.
  • Processes of the current invention also can employ cocatalyst compounds or activator compounds that are initially neutral Lewis acids but form a cationic metal complex and a noncoordinating anion, or a zwitterionic complex upon reaction with the invention compounds.
  • tris(pentafluorophenyl) boron or aluminum act to abstract a hydrocarbyl or hydride ligand to yield an invention cationic metal complex and stabilizing noncoordinating anion, see EP- A-O 427 697 and EP-A-O 520 732 for illustrations of analogous Group-4 metallocene compounds.
  • EP-A-O 495 375 For formation of zwitterionic complexes using analogous Group 4 compounds, see U.S.
  • transition metal compound does not contain at least one hydride or hydrocarbyl ligand but does contain at least one functional group ligand, such as chloride, amido or alkoxy ligands, and the functional group ligand(s) are not capable of discrete ionizing abstraction with the ionizing, anion pre-cursor compounds
  • these functional group ligands can be converted via known alkylation reactions with organometallic compounds such as lithium or aluminum hydrides or alkyls, alkylalumoxanes, Grignard reagents, etc.
  • Activators are typically strong Lewis-acids which may play either the role of ionizing or non-ionizing activator. Activators previously described as ionizing activators may also be used as non-ionizing activators.
  • Abstraction of formal neutral ligands may be achieved with Lewis acids that display an affinity for the formal neutral ligands. These Lewis acids are typically unsaturated or weakly coordinated.
  • non-ionizing activators may include R 1 O (R") 3 , where R 10 is a group 13 element and R 11 is a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, or a functional group. Typically, R 1 ' is an arene or a perfluorinated arene.
  • Non-ionizing activators may also include weakly coordinated transition metal compounds such as low valence olefin complexes.
  • Non-limiting examples of non-ionizing activators include BMe 3 , BEt 3 , B(iBu) 3 , BPh 3 , B(C 6 Fs) 3 , AlMe 3 , AlEt 3 , Al(iBu) 3 , AlPh 3 , B(C 6 F 5 ) 3 , alumoxane, CuCl,
  • Ni(1 ,5-cyclooctadiene) 2 Ni(1 ,5-cyclooctadiene) 2 .
  • Illustrative non-ionizing activators include R 10 (R ⁇ ) 3 , where R 10 is a group
  • R 11 is a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, or a functional group.
  • R 11 is an arene or a perfluorinated arene.
  • non-ionizing activators include B(R 12 ) 3 , where R 12 is an arene or a perfluorinated arene. Even more non-ionizing activators include B(C 6 H 5 ) 3 and
  • B(C 6 Fs) 3 A particularly preferred non-ionizing activator is B(C 6 Fs) 3 . More preferred activators are ionizing and non-ionizing activators based on perfluoroaryl borane and perfluoroaryl borates such as PhNMe 2 H + B(C 6 Fs) 4 " ,
  • the catalyst-precursor-to-activator molar ratio may be any ratio.
  • Combinations of the described activator compounds may also be used for activation.
  • tris(perfluorophenyl) boron can be used with methylalumoxane.
  • the precursor compounds and the activator are combined in ratios of about 1000:1 to about 0.5:1.
  • the precursor compounds and the activator are combined in a ratio of about 300: 1 to about 1 :1, alternatively about 150: 1 to about 1 :1, for boranes, borates, aluminates, etc. the ratio is about
  • alkyl aluminum compounds such as diethylaluminum chloride combined with water
  • the ratio is about 0.5:1 to about 10: 1.
  • the ratio of the first catalyst precursor compound to the second or additional catalyst precursor compounds is 5:95 to 95:5, alternatively 25:75 to 75:25, in other embodiment 40:60 to 60:40.
  • the catalyst compositions of this invention may include a support material or carrier.
  • the one or more catalyst components and/or one or more activators may be deposited on, contacted with, vaporized with, bonded to, or incorporated within, adsorbed or absorbed in, or on, one or more supports or carriers.
  • the support material is any of the conventional support materials.
  • the supported material may be a porous support material, for example, talc, inorganic oxides and inorganic chlorides.
  • Other support materials may include resinous support materials such as polystyrene, functionalized or crosslinked organic supports, such as polystyrene divinyl benzene polyolefins or polymeric compounds, zeolites, clays, or any other organic or inorganic support material and the like, or mixtures thereof.
  • Illustrative support materials such as inorganic oxides include Group 2, 3, 4, 5, 13 or 14 metal oxides.
  • the preferred supports include silica, which may or may not be dehydrated, fumed silica, alumina (see, for example, WO 99/60033), silica-alumina and mixtures thereof.
  • Other useful supports include magnesia, titania, zirconia, magnesium chloride (U.S. Pat. No. 5,965,477), montmorillonite (European Patent EP-Bl 0 511 665), phyllosilicate, zeolites, talc, clays (U.S. Pat. No. 6,034,187) and the like.
  • 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 Bl, which is incorporated herein by reference.
  • Other support materials include nanocomposites as disclosed in WO 99/47598, aerogels as disclosed in WO 99/48605, spherulites as disclosed in U.S. Pat. No. 5,972,510 and polymeric beads as disclosed in WO 99/50311.
  • the support material such as an inorganic oxide, may have a surface area in the range of from about 10 to about 700 m 2 /g, pore volume in the range of from about 0.1 to about 4.0 cc/g and average particle size in the range of from about 5 to about 500 ⁇ m.
  • the surface area of the support material may be in the range of from about 50 to about 500 m 2 /g, pore volume of from about 0.5 to about 3.5 cc/g and average particle size of from about 10 to about 200 ⁇ m.
  • the surface area of the support material may be in the range from about 100 to about 400 m 2 /g, pore volume from about 0.8 to about 3.0 cc/g and average particle size is from about 5 to about 100 ⁇ m.
  • the average pore size of the carrier of the invention typically has pore size in the range of from 10 to 1000 A, alternatively 50 to about 500 A 5 and in some embodiment 75 to about 350 A.
  • the polymerization processes of the invention may be carried out in solution, in bulk, in suspension, in gas-phase, in slurry-phase, as a high-pressure process, or any combinations thereof. Generally solution, gas-phase and slurry- phase processes are preferred. The processes may be carried out in any one or more stages and/or in any one or more reactors having any one or more reaction zones.
  • certain polyethylenes can be made using a gas phase polymerization process, e.g., utilizing a fluidized bed reactor.
  • This type reactor and means for operating the reactor are well known and completely described in, for example, U.S. Patent Nos. 3,709,853; 4,003,712; 4,011,382; 4,302,566; 4,543,399; 4,882,400; 5,352,749; 5,541,270; EP-A- 0 802 202 and Belgian Patent No. 839,380.
  • These patents disclose gas phase polymerization processes wherein the polymerization medium is either mechanically agitated or fluidized by the continuous flow of the gaseous monomer and diluent.
  • a polymerization process may be effected as a continuous gas phase process such as a fluid bed process.
  • a fluid bed reactor may comprise a reaction zone and a so-called velocity reduction zone.
  • the reaction zone may comprise a bed of growing polymer particles, formed polymer particles and a minor amount of catalyst particles fluidized by the continuous flow of the gaseous monomer and diluent to remove heat of polymerization through the reaction zone.
  • some of the re-circulated gases may be cooled and compressed to form liquids that increase the heat removal capacity of the circulating gas stream when readmitted to the reaction zone.
  • a suitable rate of gas flow may be readily determined by simple experiment.
  • Make up of gaseous monomer to the circulating gas stream is at a rate equal to the rate at which particulate polymer product and monomer associated therewith is withdrawn from the reactor and the composition of the gas passing through the reactor is adjusted to maintain an essentially steady state gaseous composition within the reaction zone.
  • the gas leaving the reaction zone is passed to the velocity reduction zone where entrained particles are removed. Finer entrained particles and dust may be removed in a cyclone and/or fine filter.
  • the gas is passed through a heat exchanger wherein the heat of polymerization is removed, compressed in a compressor and then returned to the reaction zone.
  • a slurry polymerization process can also be used.
  • a slurry polymerization process generally uses pressures in the range of from 1 to 50 atmospheres and even greater and temperatures in the range of O 0 C to 12O 0 C, and more particularly from 3O 0 C to 100 0 C.
  • a suspension of solid, particulate polymer is formed in a liquid polymerization diluent medium to which ethylene and comonomers and often hydrogen along with catalyst are added.
  • the suspension including diluent is intermittently or continuously removed from the reactor where the volatile components are separated from the polymer and recycled, optionally after a distillation, to the reactor.
  • the liquid diluent employed in the polymerization medium is typically an alkane having from 3 to 7 carbon atoms, a branched alkane in one embodiment.
  • the medium employed should be liquid under the conditions of polymerization and relatively inert. When a propane medium is used the process must be operated above the reaction diluent critical temperature and pressure. In one embodiment, a hexane, isopentane or isobutane medium is employed.
  • Hydrogen gas is often used in olefin polymerization to control the final properties of the polyolefin, such as described in Polypropylene Handbook 76-78 (Hanser Publishers, 1996).
  • MFR melt flow rate
  • MI melt index
  • MFR or MI melt index
  • the polyolefin is produced using a staged gas phase reactor.
  • a staged gas phase reactor Such polymerization systems are described in, for example, 2 Metallocene-Based Polyolefins 366-378 (John Scheirs & W. Kaminsky, eds. John Wiley & Sons, Ltd. 2000); U.S. Patent Nos. 5,665,818, 5,677,375; 6,472,484; EP 0 517 868 and EP-A-O 794 200.
  • process aid processing aid and polymer processing aid are used interchangeably and is given the broadest definition including but not limited to any commercially available process aid or any additive that can aid the extrusion and processing of a polymer resin including, but not limited to, for example, carboxylate metal salts.
  • carboxylate metal salts for example, carboxylate metal salts.
  • Carboxylate metal salts are well known in the art as additives for use with polyolefins. It has been surprisingly found that films of the present invention formed in the presence of metal stearates show improved quality as compared to films produced from commercial processing aids. Aspects of the improved quality include, but are not limited to, reduced melt fracture, reduced head pressure, reduced motor load, increased gloss and reduced haze, increased thermal stability and increased color stability.
  • carboxylate metal salt is any mono- or di- or tri-carboxylic acid salt with a metal portion from the Periodic Table of Elements.
  • Non-limiting examples include saturated, unsaturated, aliphatic, aromatic or saturated cyclic carboxylic acid salts where the carboxylate ligand has from 2 to 24 carbon atoms, such as acetate, propionate, butyrate, valerate, pivalate, caproate, isobuytlacetate, t-butyl-acetate, caprylate, heptanate, pelargonate, undecanoate, oleate, octoate, palmitate, myristate, margarate, stearate, arachate and tercosanoate.
  • Non-limiting examples of the metal portion includes a metal from the Periodic Table of Elements selected from the group of Al, Mg, Ca, Sr, Sn, Ti, V, Ba, Zn, Cd, Hg, Mn, Fe, Co, Ni, Pd, Li and Na.
  • the carboxylate metal salt is represented by the following general formula: M(Q)x (OOCR)y
  • M is a metal from Groups 1 to 16 and the Lanthanide and Actinide series, preferably from Groups 1 to 7 and 13 to 16, more preferably from Groups 3 to 7 and 13 to 16, even more preferably Groups 2 and 13, and most preferably Group 13
  • Q is halogen, hydrogen, a hydroxy or hydroxide, alkyl, alkoxy, aryloxy, siloxy, silane or sulfonate group
  • R is a hydrocarbyl radical having from 2 to 100 carbon atoms, preferably 4 to 50 carbon atoms
  • x is an integer from 0 to 3 and y is an integer from 1 to 4 and the sum of x and y is equal to the valence of the metal.
  • y is an integer from 1 to 3, preferably 1 to 2, especially where M is a Group 13 metal.
  • Non-limiting examples of R in the above formula include hydrocarbyl radicals having 2 to 100 carbon atoms that include alkyl, aryl, aromatic, aliphatic, cyclic, saturated or unsaturated hydrocarbyl radicals.
  • R is a hydrocarbyl radical having greater than or equal to 8 carbon atoms, preferably greater than or equal to 12 carbon atoms and more preferably greater than or equal to 17 carbon atoms.
  • R is a hydrocarbyl radical having from 17 to 90 carbon atoms, preferably 17 to 72, and most preferably from 17 to 54 carbon atoms.
  • Non-limiting examples of Q in the above formula include one or more, same or different, hydrocarbon containing group such as alkyl, cycloalkyl, aryl, alkenyl, arylalkyl, arylalkenyl or alkylaryl, alkylsilane, arylsilane, alkylamine, arylamine, alkyl phosphide, alkoxy having from 1 to 30 carbon atoms.
  • the hydrocarbon containing group may be linear, branched, or even substituted.
  • Q in one embodiment is an inorganic group such as a halide, sulfate or phosphate.
  • carboxylate metal salts may be aluminum carboxylates such as aluminum mono, di- and tri- stearates, aluminum octoates, oleates and cyclohexylbutyrates.
  • the carboxylate metal salt is (CH 3 (CH 2 )I 6 COO) 3 Al, a aluminum tri-stearate, (CH 3 (CH 2 )i 6 COO) 2 — Al-OH, a aluminum di-stearate, and a CH 3 (CH 2 )i 6 COO ⁇ Al(OH) 2 , an aluminum mono-stearate.
  • carboxylate metal salts may be zinc carboxylates such as zinc mono, and di-stearates, zinc octoates, oleates and cyclohexylbutyrates.
  • the carboxylate metal salt is (CH 3 (CH 2 ) I6 COO) 2 Zn, a zinc di-stearate, and a CH 3 (CH 2 )i 6 COO ⁇ Zn(OH), a zinc mono-stearate.
  • carboxylate metal salts may be calcium carboxylates such as calcium mono, and di-stearates, calcium octoates, oleates and cyclohexylbutyrates.
  • the carboxylate metal salt is (CH 3 (CH 2 )I 6 COO) 2 Ca, a calcium di-stearate, and a CH 3 (CH 2 ) I6 COO-Ca(OH), a calcium mono-stearate.
  • the carboxylate metal salt has a melting point from about 30° C to about 250° C, more preferably from about 37° C to about 220° C, even more preferably from about 50° C to about 200° C, and most preferably from about 100° C to about 200° C.
  • carboxylate metal salts include titanium stearates, tin stearates, magnesium stearates, sodium stearates boron stearate and strontium stearates.
  • the LLDPE or mLLDPE may be blended with any combination carboxylate metal salts in an amount sufficient to achieve the desired properties, such as reduction in melt fracture, reduction in motor load, extruder pressure, haze level, reblock gloss, thermal stability, and color stability.
  • one or more carboxylate metal salts may be present in the LLDPE from 0.01 to 10 weight percent in one embodiment, and from 0.01 to 5 weight percent in another embodiment, and from 0.05 to 5 weight percent in yet another embodiment, wherein a desirable range may include any combination of any upper weight percent limit with any lower weight percent limit.
  • Antioxidants and stabilizers such as organic phosphites, hindered amines, and phenolic antioxidants may also be present in the LLDPE or mLLDPE composition of the present invention. Suitable levels range from 0.001 to 5 weight percent in one embodiment, from 0.01 to 0.8 weight percent in another embodiment, and from 0.02 to 0.5 weight percent in yet another embodiment. Other common additives in the polyolefin industry may be present in LLDPE or mLLDPE composition from 0.01 to 50 weight percent in one embodiment, and from 0.1 to 20 weight percent in another embodiment, and from 1 to 5 weight percent in yet another embodiment, wherein a desirable range may include any combination of any upper weight percent limit with any lower weight percent limit.
  • the LLDPE or mLLDPE composition may further contain additives such as slip, antiblock, antioxidants, pigments, fillers, antifog, UV stabilizers, antistats, neutralizers, lubricants, surfactants, pigments, dyes and nucleating agents.
  • additives such as slip, antiblock, antioxidants, pigments, fillers, antifog, UV stabilizers, antistats, neutralizers, lubricants, surfactants, pigments, dyes and nucleating agents.
  • Ono- limiting examples include silicon dioxide, synthetic silica, titanium dioxide, polydimethylsiloxane, calcium carbonate, talc, BaSO 4 , diatomaceous earth, wax, carbon black, flame retarding additives, low molecular weight resins, hydrocarbon resins, glass beads and the like.
  • the additives may be present in the typically effective amounts well known in the art, such as 0.001 weight % to 10 weight %.
  • Fillers may be present from 0.1 to 50 weight percent in one embodiment, and from 0.1 to 25 weight percent of the composition in another embodiment, and from 0.2 to 10 weight percent in yet another embodiment.
  • Desirable fillers include, but are not limited to, titanium dioxide, silicon carbide, silica (and other oxides of silica, precipitated or not), antimony oxide, lead carbonate, zinc white, lithopone, zircon, corundum, spinel, apatite, Barytes powder, barium sulfate, magnesiter, carbon black, dolomite, calcium carbonate, talc and hydrotalcite compounds of the ions Mg, Ca, or Zn with Al, Cr or Fe and CO 3 and/or HPO 4 , hydrated or not; quartz powder, hydrochloric magnesium carbonate, glass fibers, clays, alumina, and other metal oxides and carbonates, metal hydroxides, chrome, phosphorous and brominated flame retardants, antimony trioxide, silica, silicone, and blends thereof
  • Film and resin properties can be measured by techniques well known in the art, and specifically described in the Examples herein. It has been surprisingly found that resins show enhanced thermal stability and enhanced color stability in the presence of metal carboxylates. Furthermore, it has been surprisingly found that films of the present invention formed in the presence of metal carboxylates show improved quality as compared to films produced from commercial processing aids. Aspects of the improved film quality include, but are not limited to, reduced melt fracture, reduced head pressure, reduced motor load, increased gloss and reduced haze. Aspects of the improved film quality include, but are not limited to, thermal stability and enhanced color stability.
  • Heat seal and hot tack measurements were made according to the following procedure.
  • the films were conditioned for heat seal and hot tack measurements by aging the samples for at least 40 hours at 23 °C and 50% humidity before testing.
  • a Heatsealer (Model PC, available from Theller) was used to measure the heat seal characteristics of the films.
  • the samples were cut into 20.3 cm by 15.2 cm (8 inch by 6 inch) sheets and sandwiched between Mylar sheets so that the inside surfaces of the blown films were in contact.
  • the seal was created by placing the Mylar-covered films were between 12.7 cm (5 inch) long seal bars and a pressure of 0.5 MPa (73 psi) was applied for 1.0 seconds.
  • Seals were created at temperatures ranging from 75°C to 150°C, and the seal length was approximately 25.4 mm (1 inch). The heat seals were then aged for a minimum of 24 hours at 23 C and 50% humidity and the seal strength was measured at a rate of 508 mm/min (20 inch/min). Hot tack curves were generated on a J&B Instruments hot tack tester using 15-mm wide film samples backed with 50 mm thick PET tape. The seal time and pressure was 0.5 s and 0.5 MPa, respectively. The seal strength was measured after 0.4 s delay time at a speed of 200 mm/min.
  • the molecular weights and molecular weight distributions of the resins described in the present invention were characterized using a High Temperature Size Exclusion Chromatograph (PL 220, Polymer Laboratories), equipped with a differential refractive index detector (DRI). Three Polymer Laboratories PL gel 10mm Mixed-B columns were used. The nominal flow rate was 1.0 cm 3 /min, and the nominal injection volume was 300 mL. The various transfer lines, columns and differential refractometer (the DRI detector) were contained in an oven maintained at 140 0 C.
  • PL 220 High Temperature Size Exclusion Chromatograph
  • DRI detector differential refractive index detector
  • Polymer solutions were prepared in filtered 1,2,4-Trichlorobenzene (TCB) containing 1000 ppm of butylated hydroxy toluene (BHT). The same solvent was used as the SEC eluent. Polymer solutions were prepared by dissolving the desired amount of dry polymer in the appropriate volume of SEC eluent to yield concentrations ranging from 0.5 to 1.5 mg/mL. The sample mixtures were heated at 140 0 C with continuous agitation for about 2 to 2.5 hours. Sample solution will be filtered off-line before injecting to GPC with 2 ⁇ m filter using the Polymer Labs SP260 Sample Prep Station.
  • the separation efficiency of the column set was calibrated using a series of narrow MWD polystyrene standards, which reflects the expected MW range for samples and the exclusion limits of the column set. Eighteen individual polystyrene standards, ranging from Mp ⁇ 580 to 10,000,000, were used to generate the calibration curve. The polystyrene standards are obtained from Polymer Laboratories (Amherst, MA). To assure internal consistency, the flow rate is corrected for each calibrant run to give a common peak position for the flow rate marker (taken to be the positive inject peak) before determining the retention volume for each polystyrene standard. The flow marker peak position thus assigned was also used to correct the flow rate when analyzing samples therefore, it is an essential part of the calibration procedure.
  • a calibration curve (log Mp vs. retention volume) is generated by recording the retention volume at the peak in the DRI signal for each PS standard, and fitting this data set to a 2nd- order polynomial.
  • the equivalent polyethylene molecular weights are determined by using the following Mark-Houwink coefficients:
  • Films may be formed by any number of well known extrusion or coextrusion techniques. Any of the blown or chill roll techniques commonly used are suitable.
  • the composition can be extruded in a molten state through a flat die and then cooled to form a film.
  • the composition can be extruded in a molten state through an annular die and then blown and cooled to form a tubular, blown film, which can then be axially slit and unfolded to form a flat film.
  • Films of the invention may be unoriented, uniaxially oriented or biaxially oriented. Physical properties of the film may vary from those of the polymer blend, depending on the film forming techniques used.
  • the granular EXCEED 1018 SB feedstock was formulated with 0.05 % IRGANOX 1076, 0.2 % WESTON 399, and 0.5% OPTIBLOCK 10.
  • Compounding and of the resins was carried out on a Werner & Pfleiderer ZSK 57rnm twin screw extruder under a nitrogen blanket. Output rate was 68.1 kg/h (150 Ib/h) and the melt temperature was about 210°C.
  • a purge/ cleaning resin was formulated with 5% diatomaceous earth instead of the OPTIBLOCK 10.
  • Output rate was 3.36 kg/mm (188 lb/in) (or 7 g/mm/mm (10 lb/in/in) die circumference).
  • the specific extrusion conditions are listed in Tables 7 and 8.
  • the master batch was added by dry blending in a double cone mixer prior to film production.
  • the Aluminum Stearate was from the same batch as used for the Gloucester film trials described below.
  • Table 1 below lists the resin formulations for the purge/cleaning resin containing 5% diatomaceous earth.
  • EXAMPLE 3 Film Blowing Sano Line - films were made on the Sano film line using two different settings: die gaps of 40 and 60 mil, output rates of 8 and 10 lb/hr/inch die, and melt temperature of 395 and 420 0 F, respectively.
  • the target film gauge was 1 mil for all films. Details and run conditions for each film are listed in Table 2 below.
  • the time to obtain completely melt fracture free film was about 40 minutes for calcium stearate CaSt and zinc stearate (ZnSt) containing resins and about 20 min for the samples with aluminum Stearate (AlSt) and DYNAMAR FX5920A.
  • the films form the purge resin showed severe melt fracture and grey color 5 to 10 minutes after it was fed. Melt fracture remained 100% for at least 1 hour after the control #1 resin was introduced.
  • Table 2 shows the process conditions for the experimental films as well as control resin #1. The data for the experimental samples reflect the process conditions of step 3 from the above procedure, i.e., after running the purge resin and the control resin #1 for 1 hour each. The only slight deviation from this procedure was the ZnSt containing resin, 00270-134-032, which was introduced after 2 hours of running control #1 resin. The data was recorded after one hour after all parameters stabilized.
  • Film properties - The film properties of the AlSt films differ somewhat from the other samples. Dart impact strength of the AlSt film is about 20% lower than that of the film with DYNAMAR FX5920A. The AlSt film shows the best optical properties with haze of about 7% while other surface properties, such as friction coefficient or Reblock are similar.
  • Table 3 lists the mechanical properties from the first Sano trial. The mechanical properties of the CaSt, ZnSt and DYNAMAR FX5920A films are similar
  • Second Sano run 60 mil die gap / 420 0 F / 10 lbs/in die
  • This second trial was conducted to determine if higher metal stearate concentrations (0.2%) and higher extrusion temperatures lead to die lip build-up or significant changes in the film's properties.
  • two stearate resins with 0.2% ZnSt, and 0.2% CaSt, respectively were prepared using the masterbatch and dry blending in a double cone mixer prior to film production.
  • the CaSt and ZnSt containing resins were run for 4 hours each. After 8 hours of operation with 0.2% of a metal stearate, there was no visible build-up on the die exit.
  • Table 5 shows the process conditions for the second Sano trial and Table 6 comparing mechanical data. The only notable difference is a lower reblock value of the films with higher ZnSt concentration. All other properties are very similar. Heat seal properties of the film with 0.2% ZnSt are included in FIGs. 3 and 4. There is practically no difference to the films with 0.1% ZnSt concentration. High melt temperature and longer run duration did not result in die lip build-up. TABLE 5
  • the metal stearate and DYNAMAR FX5920 was added to the respective resin during the compounding step along with the IRGANOX 1076 (0.05%), WESTON 399 (0.2 %), and OPTIBLOCK 10 (0.5 %).
  • the base resin was granular EXCEED 1018 SB. Compounding and pelleting was done on a ZSK 57 mm twin-screw extruder under a nitrogen blanket. The purge/cleaning resin contained 5% diatomaceous earth rather than OPTIBLOCK 10.
  • Film properties of the films from the second trial are listed in Tables 10 and 11. Specifically, Table 10 indicates mechanical film properties and Table 11 indicates optical and surface film properties for the second Gloucester trial. Films containing metal stearate show better optical properties and about 20 % lower dart impact strength than the film with DYNAMAR FX5920. Other properties are very similar and the differences are not statistically significant.
  • the samples for the thermal and color stability tests were obtained according to the following procedure: (1) The granular formulation was introduced into the extruder and a minimum of 10 lbs. were purged prior to capturing a sample of the compounded resin (extrusion pass 0); (2) The compounded resin from step (1) was reintroduced in the extruder and subjected to another extrusion pass (pass 1). The sample was taken after 3 lbs. of resin ran through the extruder to purge it; and (3) The resin from extrusion pass 1 was reintroduced in the extruder and subjected to another extrusion pass (pass 2). A sample was taken after 3 lbs. of resin ran through the extruder to purge it.
  • Table 15 shows melt index (I 2 ), high load melt index (I 2 ]), melt index ratio (I 2 i/I 2 ) and yellowness index (YI) of the formulations listed in Table 12 after extrusion passes 1,2,3, and 5.
  • I 2 melting index
  • I 2 i flow index
  • YI yellowness index
  • Table 15 displays the melt index data of samples designated as 00332-009- 603 and 00332-009-604.
  • the formulations with zinc stearate provide for much better melt index stability than the formulations with less (and without) zinc stearate after each extrusion pass.
  • the formulations with zinc stearate provide for a constant melt index ratio (I 2 i /I 2 ) after each extrusion pass while the formulations with less zinc stearate show a significant increase in melt index ratio.
  • the zinc stearate containing formulations (Examples 00332-009-603 and 00332-009-604) also provide acceptable color stability.
  • ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited.
  • ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited.
  • within a range includes every point or individual value between its end points even though not explicitly recited. Thus, every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

L'invention porte sur un procédé pour la transformation d'une composition de polyoléfine en un film, le procédé comprenant la mise en contact d'un polyéthylène basse densité linéaire (LLDPE) avec une quantité suffisante d'un sel métallique pour réduire, par exemple, les marques de coulée, le LLDPE présentant une masse moléculaire (Mw) de 50 000 g/mol à 180 000 g/mol, une distribution de la masse moléculaire de 1,5 à 3,0 et un indice de fluage à chaud de 15 à 25, ainsi que sur le traitement en phase fondue du LLDPE et du sel métallique pour former le film. L'invention porte également sur des compositions de polyoléfine traitées à l'aide de sels métalliques.
PCT/US2009/002934 2008-05-15 2009-05-12 Compositions de polyoléfine et procédés de traitement de celles-ci à l'aide de sels métalliques WO2009139851A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024079553A1 (fr) * 2022-10-11 2024-04-18 Nova Chemicals (International) S.A. Sel métallique en tant qu'auxiliaire de traitement de polymère

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0526117A1 (fr) * 1991-07-31 1993-02-03 BP Chemicals Limited Compositions d'additifs pour polymères
WO2000002930A1 (fr) * 1998-07-10 2000-01-20 Univation Technologies Llc Composition catalytique, ses procedes de preparation et son application dans le procede de polymerisation
US20080038533A1 (en) * 2006-05-31 2008-02-14 Best Steven A Linear polymers, polymer blends, and articles made therefrom
WO2009082546A2 (fr) * 2007-12-18 2009-07-02 Exxonmobil Chemical Patents Inc. Films de polyéthylène et procédé pour leur production

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0526117A1 (fr) * 1991-07-31 1993-02-03 BP Chemicals Limited Compositions d'additifs pour polymères
WO2000002930A1 (fr) * 1998-07-10 2000-01-20 Univation Technologies Llc Composition catalytique, ses procedes de preparation et son application dans le procede de polymerisation
US20080038533A1 (en) * 2006-05-31 2008-02-14 Best Steven A Linear polymers, polymer blends, and articles made therefrom
WO2009082546A2 (fr) * 2007-12-18 2009-07-02 Exxonmobil Chemical Patents Inc. Films de polyéthylène et procédé pour leur production

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024079553A1 (fr) * 2022-10-11 2024-04-18 Nova Chemicals (International) S.A. Sel métallique en tant qu'auxiliaire de traitement de polymère

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