Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/22—Organic complexes
  • B01J31/2282—Unsaturated compounds used as ligands
  • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
  • B01J2531/48—Zirconium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
  • B01J2531/49—Hafnium
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer

Definitions

• the present invention relates to processes for polymerizing olefin(s) to produce polymers having improved properties. Also, the invention is directed to a metallocene catalyst compound and catalyst system for use in the polymerization of olefin(s) to produce polymers having improved properties. In particular, the invention is directed to cyclic bridged metallocene catalyst systems, their use in a polymerization process, and products produced therefrom.
• Processability is the ability to economically process and shape a polymer uniformly. Processability involves such elements as how easily the polymer flows, melt strength, and whether or not the extrudate is distortion free.
• Typical metallocene catalyzed polyethylenes mPE are somewhat more difficult to process than low-density polyethylenes (LDPE) made in a high-pressure polymerization process.
• LDPE low-density polyethylenes
• mPEs require more motor power and produce higher extruder pressures to match the extrusion rate of LDPEs.
• Typical mPEs also have lower melt strength which, for example, adversely affects bubble stability during blown film extrusion, and they are prone to melt fracture at commercial shear rates.
• mPEs exhibit superior physical properties as compared to LDPEs.
• 0004 It is not unusual in the industry to add various levels of an LDPE to an mPE to increase melt strength, to increase shear sensitivity, i.e., to increase flow at commercial shear rates; and to reduce the tendency to melt fracture.
• these blends generally have poor mechanical properties as compared with neat mPE.
• metallocene catalysts produce polymers having a narrow molecular weight distribution. Narrow molecular weight distribution polymers tend to be more difficult to process. The broader the polymer molecular weight distribution the easier the polymer is to process.
• a technique to improve the processability of mPEs is to broaden the products' molecular weight distribution (MWD) by blending two or more mPEs with significantly different molecular weights, or by changing to a polymerization catalyst or mixture of catalysts that produce broad MWD polymers.
• MWD molecular weight distribution
• 5,470,81 1 describes the use of a mixture of metallocene catalysts for producing easy processing polymers. Also, U.S. Patent No. 5,798,427 addresses the production of polymers having enhanced processability using a metallocene catalyst compound where the ligands are specifically substituted indenyl ligands.
• U.S. Patent No. 6,339,134 (Crowther et al.) and U.S. Patent No. 6,388,1 15 (Crowther et al.), describe a ligand metallocene catalyst compound represented by the formula L A L B MQ n , where MQ n may be, among other things, zirconium dichloride, and L A and L B may be, among other things, open, acyclic, or fused ring(s) or ring system(s) such as unsubstituted or substituted, cyclopentadienyl ligands or cyclopentadienyl-type ligands, heteroatom substituted and/or heteroatom containing cyclopentadienyl-type ligands.
• MQ n may be, among other things, zirconium dichloride
• L A and L B may be, among other things, open, acyclic, or fused ring(s) or ring system(s) such
• the Q ligands include hydrocarbyl radicals having from 1 to 20 carbon atoms.
• 00081 Particularly useful ligand metallocenes for improving processability contain cyclic bridges connecting ligands L A and L B .
• Supported catalysts prepared from these metallocenes, as reported in U.S. Patent No. 6,339,134 (Crowther et al.) and U.S. Patent No. 6,388,115 ⁇ Crowther et al.), suffer from low productivities (max prod 1066 g polymer /g supported cat x h) in gas-phase polymerizations.
• PCT Publication No. WO 03/064433 (Holtcamp, M.W.), relates to polymerization catalyst activator compounds that are either neutral or ionic and include a Group 13 atom, preferably boron or aluminum, bonded to at least one halogenated or partially halogenated heterocyclic ligand.
• the publication states that such activator compounds may be used to activate metallocene catalyst compositions. Two metallocenes, with cyclic bridges connecting ligands L A and L B were separately examined in with this activator in solution.
• This invention relates generally to polymerization processes utilizing a cyclic bridged metallocene catalyst for producing polymer products that have improved properties. Also, the invention is directed to improve bridged metallocene catalyst compounds having a cyclic bridge, catalyst systems comprising these compounds, and polymerizing processes utilizing these compounds.
• an olefin polymerization catalyst system comprising a cyclic bridged metallocene, L A (R'SiR')L B ZrQ 2 , activated by an activator, the activator comprising an aluminoxane and supported by a support.
• the cyclic bridged metallocene, L A (R'SiR')L B ZrQ 2 is comprised of L A and L B connected to one another with a cyclic silicon bridge, R' SiR', where each R' are independently hydrocarbyl or substituted hydrocarbyl substituents that are connected with each other to form a silacycle ring.
• Each of the ligands is bound to a zirconium atom.
• Ligands L ⁇ and L B are unsubstituted or substituted cyclopentadienyl ligands as described by the formula (C 5 H 4 .dRd), where d is an integer selected from 0, 1 , 2, 3 or 4 and R is hydrogen, a hydrocarbyl substituent, a substituted hydrocarbyl substituent or a heteroatom substituent.
• the two leaving groups Q are labile hydrocarbyl or substituted hydrocarbyl ligands.
• support or “carrier” are used interchangeably and are any support material, preferably a porous support material, for example, talc, inorganic oxides and inorganic chlorides.
• Other carriers 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.
• the catalyst system may be formed by first combining the activator with the support, and then by adding thereto the L A (R'SiR')L B ZrQ 2 .
• the catalyst system may be used in the making of a polymer comprising, as monomers, ethylene, an olefin monomer having from 3 to 8 carbon atoms, and optionally one or more other olefin monomers having from 2 to 30 carbon atoms such as, hexane or butene.
• the use may be for controlling product melt index, for controlling molecular weight distribution, or for controlling film haze.
• the polymer product may have a density of 0.910 to 0.945 g/cc, or 0.915 to 0.935 g/cc.
• the catalyst system may be used for producing a polymer product with broad or bimodal distribution in molecular weight or melt index, in a single reactor, comprising, as monomers, ethylene, an olefin monomer having from 3 to 8 carbon atoms, and optionally one or more other olefin monomers having from 2 to 30 carbon atoms, by changing comonomer, terpolymer, or polymer ratio in a controlled manner.
• the catalyst system may be used for producing a polymer product with broad or bimodal distribution in density in a single reactor, comprising, as monomers, ethylene, an olefin monomer having from 3 to 8 carbon atoms, and optionally one or more other olefin monomers having from 2 to 30 carbon atoms, in a controlled manner.
• the monomers may be ethylene and butene.
• the monomers may be ethylene, butene and at another olefin monomer having from 2 to 30 carbon atoms.
• the polymer product may have a molecular weight distribution (Mw/Mn) of no greater than about 4.2, or about 3.6 to about 4.2.
• the invention relates to the manufacture of a high productivity cyclic bridged metallocene supported catalyst for the production of polymers from ethylene and other olefins.
• the cyclic bridged metallocene catalyst comprises (CH 2 ) 4 Si(C 5 Me 4 )(C 5 H 4 )Zr(CH 3 ) 2 , methyl aluminoxane and silica (average particle size of 40 ⁇ , average surface area 300 m 2 /g, dehydrated at 600°C). This catalyst system was highly productive for manufacture of copolymers of ethylene and butene in a gas-phase process.
• the productivity of at least 1786 g Polymer/ (g cat h) or greater at 70 0 C and 170 psi partial pressure of ethylene was greater than any productivity previously seen for supported cyclic-bridged metallocene in a slurry or gas-phase process. This higher productivity is even under adverse conditions of lower ethylene partial pressure and temperature than in previously described systems.
• Figs. 1 and 2 contain graphs of strain hardening of an HP-LDPE ExxonMobil LD 103.09 polymer; and a polymer made using (C 4 H 8 )Si(C 5 Me 4 )(C 5 H 4 )ZrMe 2 as the catalyst, respectively.
• Fig. 3 is a graph of MFR v. MI for polymers of embodiments of the instant invention and comparative polymers.
• Fig. 4 is a graph of Area Retramat shrinkage v. MD Plastic Tension for polymers of embodiments of the instant invention and comparative polymers.
• Fig. 5 is a graph of g 1 v. molecular weight for polymers of embodiments of the instant invention and comparative polymers.
• 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.
• Cyclic bridged metallocene catalysts according to an embodiment of the instant invention are comprised of a cyclic bridged metallocene, as shown in equation I, an activator, and a support.
• the cyclic bridged metallocenes are shown in equation I. They contain two ligands L A and L B connected to one another with a cyclic silicon bridge, R' SiR'. Each of the ligands is bound to a zirconium atom. In one preferred embodiment, at least one ligand is ⁇ -bonded to a metal atom, most preferably ⁇ 5 -bonded to the metal atom. Two leaving groups Q are bonded to the zirconium atom.
• the ligands L A and L B are unsubstituted or substituted cyclopentadienyl ligands as described by the formula (C 5 H 4 ⁇ R d ), where d is an integer selected from 0, 1, 2, 3 or 4 and R is hydrogen, a hydrocarbyl substituent, a substituted hydrocarbyl substituent or a heteroatom substituent. At least two R groups, preferably two adjacent R groups, may join to form a ring structure. Also, a substituent group R group such as 1 -butanyl may form a carbon sigma bond to zirconium.
• Hydrocarbyl substituents are made up of between 1 and 100 carbon atoms, the remainder being hydrogen.
• Non-limiting examples of hydrocarbyl substituents include linear or branched or cyclic: alkyl radicals; alkenyl radicals; alkynyl radicals; cycloalkyl radicals; aryl radicals; alkylene radicals, or a combination thereof.
• Non-limiting examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl; olefinically unsaturated substituents including vinyl-terminated ligands (for example but-3-enyl, prop-2-enyl, hex-5-enyl and the like), benzyl or phenyl groups and the like, including all their isomers, for example tertiary butyl, isopropyl, and the like.
• Substituted hydrocarbyl substituents are made up of between 1 and 100 carbon atoms, the remainder being hydrogen, fluorine, chlorine, bromine, iodine, oxygen, sulfur, nitrogen, phosphorous, boron, silicon, germanium or tin atoms.
• Substituted hydrocarbyl substituents are carbon based radicals.
• Non-limiting examples of substituted hydrocarbyl substituents trifluoromethyl radical, trimethylsilyl, trimethylsilanemethyl (Me 3 SiCH 2 -) radicals.
• Heteroatom substituents are fluorine, chlorine, bromine, iodine, oxygen, sulfur, nitrogen, phosphorous, boron, silicon, germanium or tin based radicals.
• heteroatom substituents include organometalloid radicals.
• Non-limiting examples of heteroatom substituents include, methoxy radical, diphenyl amino radical, thioalkyl, thioalkenyl, methyltrimethylsilyl radical, dimethyl aluminum radicals, tris(perflourophenyl)boron and the like.
• Non-limiting examples of ligands include cyclopentadienyl ligands, indenyl ligands, benzindenyl ligands, fluorenyl ligands, octahydrofluorenyl ligands, including hydrogenated versions thereof, for example tetrahydroindenyl ligands.
• L A and L B may be any other ligand structure capable of ⁇ -bonding to M, preferably ⁇ 3 -bonding to M, and most preferably ⁇ 5 -bonding to M.
• L A and L B may comprise one or more heteroatoms, for example, nitrogen, silicon, boron, germanium, sulfur and phosphorous, in combination with carbon atoms to form an open, acyclic, or preferably a fused, ring or ring system, for example, a hetero-cyclopentadienyl ancillary ligand.
• heteroatoms for example, nitrogen, silicon, boron, germanium, sulfur and phosphorous
• the cyclic bridged metallocene catalyst compounds are those where the R substituents on the ligands L A and L B , (C 5 H 4-c )R d ) of formula (I) is substituted with the same or different number of substituents on each of the ligands.
• the ligands L A and L B , (C 5 H 4 ⁇ R d ) of formula (I) are different from each other.
• the ligands of the metallocene catalyst compounds of formula (I) are asymmetrically substituted.
• at least one of the ligands L A and L B , (C 5 H 4-d R d ) of formula (I) is unsubstituted. More preferably, L A is C 5 Me 4 , where Me is methyl, and L B is C 5 H 4 .
• cyclic bridging groups include cyclo-tri or tetra-alkylene silyl groups.
• cyclic bridging groups are represented by the following structures:
• the silacycle ring is a 3-5 member ring. More preferably the silacycle is a 4-5 member ring. More preferred cyclic bridging groups include cyclotrimethylenesilyl or cyclotetramethylenesilyl. Most preferred is cyclotetramethylenesilyl.
• the two leaving groups Q are labile hydrocarbyl or substituted hydrocarbyl ligands.
• Q may also include hydrocarbyl groups having ethylenic or aromatic unsaturation thereby forming a ⁇ 3 bond to Zr.
• two Q's may be an alkylidene, or a cyclometallated hydrocarbyl.
• two Q's may be a coordinated diene or polyene such as butadiene or isoprene.
• Q originates from butadiene or isoprene. More preferably, Q is allyl, benzyl, trimethylsilylmethyl, or methyl. Most preferably, Q is methyl.
• the metallocene catalyst compounds of the invention include cyclotrimethylenesily ⁇ tetramethyl cyclopentadienyl)(cyclopentadienyl)zirconium dimethyl, cyclotetramethylenesilyl(tetramethyl cyclopentadienyl)(cyclopentadienyl)zirconium dimethyl, cyclotrimethylenesilyl (tetramethyl cyclopentadienyl)(2-methyl indenyl)zirconium dimethyl, cyclotrimethylenesily ⁇ tetramethyl cyclopentadienyl)(3 -methyl cyclopentadienyl)zirconium dimethyl, cyclotrimethylenesilyl bis(2-methyl indenyl)zirconium dimethyl, cyclotrimethylenesilyl(tetramethyl cyclopentadienyl)(2,3,5-trimethyl cyclopentadienyl) zi
• the above described cyclic bridged metallocene catalyst compounds can be activated with an activator comprising an aluminoxane or the product of an aluminoxane and a support or carrier. This activation yields catalyst compounds capable of polymerizing olefins.
• aluminoxanes contain a broad distribution of structures formed from the reaction of R"3A1 or mixtures of R"3 Al, where R" is hydrogen or a similar or different hydrocarbyl, with water. This is in contrast with dialuminoxanes which have a specific structure. It is also well recognized that aluminoxanes may contain alanes, R"3A1, remaining from an incomplete hydrolysis reaction.
• Activation may also occur in the presence of aluminoxanes combined in series or in parallel with other activators capable of converting cyclic bridged metallocenes into olefin polymerization catalysts.
• Non-limiting additional activators may include a Lewis acid or a non-coordinating ionic activator or ionizing activator or any other compound including Lewis bases, aluminum alkyls, conventional-type cocatalysts or an activator-support and combinations thereof that can convert a neutral metallocene catalyst compound to a catalytically active metallocene cation.
• aluminoxane or modified aluminoxane as an activator, and/or to also use ionizing activators, neutral or ionic, such as tri (n- butyl)ammonium tetrakis(pentafluorophenyl)boron or a trisperfluorophenyl boron metalloid precursor or a trisperfluoronaphtyl boron metalloid precursor that would ionize the neutral metallocene catalyst compound.
• an additional activation method using ionizing ionic compounds not containing an active proton but capable of producing both a metallocene catalyst cation and a non-coordinating anion are also contemplated, and are described in EP-A-O 426 637, EP-A- 0 573 403 and U.S. Pat. No. 5,387,568.
• Additional ionizing 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.
• WO 98/07515 such as tris (2, 2', 2"-nonafluorobiphenyl)fluoroaluminate.
• Combinations of activators are also contemplated by the invention, for example, aluminoxanes and ionizing activators in combinations, see for example, WO 94/07928 and WO 95/14044, and U.S. Patent 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. Also, methods of activation such as using radiation (see EP-Bl-O 615 981), electro-chemical 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.
• one or more metallocene catalyst compounds or catalyst systems may be used in combination with one or more conventional-type catalyst compounds or catalyst systems.
• Mixed catalysts and catalyst systems are described in U.S. Patent Nos. 4,159,965, 4,325,837, 4,701,432, 5,124,418, 5,077,255, 5,183,867, 5,391,660, 5,395,810, 5,691 ,264, 5,723,399 and 5,767,031 , and WO 96/23010.
• cyclic metallocene catalyst compounds and catalyst systems may be combined with one or more support materials or carriers using one of the support methods well known in the art or as described below.
• the method of an embodiment of the invention uses a polymerization catalyst in a supported form.
• a metallocene catalyst compound or catalyst system is in a supported form, for example deposited on, bonded to, contacted with, or incorporated within, adsorbed or absorbed in, or on, a support or carrier.
• support or “carrier” are used interchangeably and are any support material, preferably a porous support material, for example, talc, inorganic oxides and inorganic chlorides.
• Other carriers 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.
• the preferred carriers are inorganic oxides that include Group 2, 3, 4, 5, 13 or 14 metal oxides.
• the preferred supports include silica, alumina, silica-alumina, magnesium chloride, and mixtures thereof.
• Other useful supports include magnesia, titania, zirconia, montmorillonite (EP-B 1 0 511 665) and the like.
• combinations of these support materials may be used, for example, silica- chromium, silica-alumina, silica-titania and the like.
• the carrier most preferably an inorganic oxide, has 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. More preferably, the surface area of the carrier is 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 carrier is in the range is 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 embodiments of the invention may have a pore size in the range of from 10 to 1000 A, preferably 50 to about 500 A, and most preferably 75 to about 350 A.
• the cyclic bridged metallocene catalyst compounds of embodiments of the invention may be deposited on the same or separate supports together with an activator, or the activator may be used in an unsupported form, or may be deposited on a support different from the supported metallocene catalyst compounds of an embodiment of the invention, or any combination thereof.
• the cyclic bridged metallocene catalyst compound of amn embodiment of the invention may contain a polymer bound ligand as described in U.S. Patent Nos. 5,473,202 and 5,770,755
• the metallocene catalyst system of tan embodiment of the invention may be spray dried as described in U.S. Patent No. 5,648,310
• the support used with the cyclic bridged metallocene catalyst system of an embodiment of the invention is functionalized as described in European Publication No. EP-A-O 802 203, or at least one substituent or leaving group is selected as described in U.S. Patent No. 5,688,880.
• a supported cyclic bridged metallocene catalyst system that includes an antistatic agent or surface modifier that is used in the preparation of the supported catalyst system as described in PCT Publication No. WO 96/1 1960.
• the catalyst systems of an embodiment of the invention can be prepared in the presence of an olefin, for example hexene-1.
• a preferred method for producing the supported cyclic bridged metallocene catalyst system of an embodiment of the invention is described below and is described in WO 96/00245 and WO 96/00243.
• the cyclic bridged metallocene catalyst compound is slurried in a liquid to form a metallocene solution and a separate solution is formed containing an activator and a liquid.
• the liquid may be any compatible solvent or other liquid capable of forming a solution or the like with the cyclic bridged metallocene catalyst compounds and/or activator of an embodiment of the invention.
• the liquid is a cyclic aliphatic or aromatic hydrocarbon, most preferably toluene.
• the cyclic bridged metallocene catalyst compound and activator solutions are mixed together and added to a porous support or the porous support is added to the solutions such that the total volume of the metallocene catalyst compound solution and the activator solution or the metallocene catalyst compound and activator solution is less than four times the pore volume of the porous support, more preferably less than three times, even more preferably less than two times; preferred ranges being from 1.1 times to 3.5 times range and most preferably in the 1.2 to 3 times range.
• Another preferred method is to pre-react the porous support with an activator in a hydrocarbon diluent.
• the hydrocarbon solution of the cyclic bridged metallocene is added later to complete the catalyst preparation.
• the mole ratio of the metal of the activator component to the metal of the supported cyclic bridged metallocene catal yst compounds are in the range of between 0.3: 1 to 1000: 1 , preferably 20: 1 to 800: 1 , and most preferably 50: 1 to 500:1.
• the activator is an ionizing activator such as those based on the anion tetrakis(pentafluorophenyl)boron
• the mole ratio of the metal of the activator component to the metal component of the cyclic bridged metallocene catalyst is preferably in the range of between 0.3: 1 to 3:1.
• the catalyst system comprises a catalyst as described herein activated by methylaluminoxane (MAO) and supported by silica. While conventionally, MAO is combined with a metallocene and then the combination is deposited on silica, as shown in the examples, the preference herein is to first combine the activator (e.g. MAO) and the support (e.g. silica) and then to add the catalyst to the combination. Modified MAO (MMAO) or a combination of MAO and MMAO may also be used.
• MAO methylaluminoxane
• olefin(s), preferably C 2 to C 30 olefin(s) or alpha-olefin(s), preferably ethylene or propylene or combinations thereof are prepolymerized in the presence of the c yclic bridged metallocene catalyst system of an embodiment of the invention prior to the main polymerization.
• the prepolymerization can be carried out batchwise or continuously in gas, solution or slurry phase including at elevated pressures.
• the prepolymerization can take place with any olefin monomer or combination and/or in the presence of any molecular weight controlling agent such as hydrogen.
• any molecular weight controlling agent such as hydrogen.
• the cyclic bridged metallocene catalysts of embodiments of the invention can be combined with a carboxylic acid salt of a metal ester, for example aluminum carboxylates such as aluminum mono, di- and tri- stearates, aluminum octoates, oleates and cyclohexylbutyrates, as described in U.S. Patent No. 6,300,436.
• a carboxylic acid salt of a metal ester for example aluminum carboxylates such as aluminum mono, di- and tri- stearates, aluminum octoates, oleates and cyclohexylbutyrates, as described in U.S. Patent No. 6,300,436.
• the catalysts and catalyst systems of embodiments of the invention described above are suitable for use in gas-phase or slurry processes over a wide range of temperatures and pressures.
• the most preferred process is a gas phase process.
• the temperatures may be in the range of from -60°C to about 28O 0 C, preferably from 50 0 C to about 200 0 C, and the pressures employed may be in the range from 1 atmosphere to about 500 atmospheres or higher.
• the gas phase or slurry phase processes may be conducted in combination with each-other or with a high pressure or solution process.
• Particularly preferred is a gas phase or slurry phase polymerization of one or more olefins at least one of which is ethylene or propylene.
• the process of this invention is directed toward a slurry or gas phase polymerization process of one or more olefin monomers having from 2 to 30 carbon atoms, preferably 2 to 12 carbon atoms, and more preferably 2 to 8 carbon atoms.
• An Embodiment of the invention are particularly well suited to the polymerization of two or more olefin monomers of ethylene, propylene, butene-1, pentene-1, 4-methyl-pentene-l, hexene-1, octene- 1 and decene-1.
• Other monomers useful in the process of embodiments of the invention include ethylenically unsaturated monomers, diolefins having 4 to 18 carbon atoms, conjugated or nonconjugated dienes, polyenes, vinyl monomers and cyclic olefins.
• Non-limiting monomers useful in an embodiment of the invention may include norbornene, norbornadiene, isobutylene, isoprene, vinylbenzocyclobutane, styrenes, alkyl substituted styrene, ethylidene norbornene, dicyclopentadiene and cyclopentene.
• a copolymer of ethylene is produced, where with ethylene, a comonomer having at least one alpha-olefin having from 4 to 15 carbon atoms, preferably from 4 to 12 carbon atoms, and most preferably from 4 to 8 carbon atoms, is polymerized in a gas phase process.
• a copolymer of ethylene and butene is produced.
• ethylene or propylene is polymerized with at least two different comonomers, optionally one of which may be a diene, to form a terpolymer.
• two of the three monomers of the terpolymer are butene and ethylene.
• the comonomer content is 1.0 to 20.0 wt%, or 2.0 to 15.0 wt%.
• (C 4 H 8 )Si(C 5 Me 4 )(C 5 H 4 )ZrMe 2 as the catalyst in preparing an ethylene/butene copolymer, resulted in a sharp response to comonomer ratio.
• melt index changed quickly and sharply as the comonomer ratio was adjusted. Density changes were also observed. These changes may be associated with long chain branching. Therefore, polymers having ethylene and butene as two of the monomers may be used to control product melt index. Further, products with broad or bimodal distribution in molecular weight or melt index in a single reactor using a single catalyst could be used by changing the comonomer feed in a controlled fashion, thus producing polyethylene products with custom designed properties with single reactor economics.
• the invention is directed to a polymerization process, particularly a gas phase or slurry phase process, for polymerizing propylene alone or with one or more other monomers including ethylene, and/or other olefins having from 4 to 12 carbon atoms.
• Polypropylene polymers may be produced using the particularly bridged metallocene catalysts as described in U.S. Patent Nos. 5,296,434 and 5,278,264.
• a continuous cycle is employed where in one part of the cycle of a reactor system, a cycling gas stream, otherwise known as a recycle stream or fluidizing medium, is heated in the reactor by the heat of polymerization. This heat is removed from the recycle composition in another part of the cycle by a cooling system external to the reactor.
• a gas fluidized bed process for producing polymers a gaseous stream containing one or more monomers is continuously cycled through a fluidized bed in the presence of a catalyst under reactive conditions. The gaseous stream is withdrawn from the fluidized bed and recycled back into the reactor. Simultaneously, polymer product is withdrawn from the reactor and fresh monomer is added to replace the polymerized monomer.
• the reactor pressure in a gas phase process may vary from about 100 psig (690 kPa) to about 500 psig (3448 kPa), preferably in the range of from about 200 psig (1379 kPa) to about 400 psig (2759 kPa), more preferably in the range of from about 250 psig (1724 kPa) to about 350 psig (2414 kPa).
• the reactor temperature in a gas phase process may vary from about 30°C to about 120°C, preferably from about 60 0 C to about 115°C, more preferably in the range of from about 70°C to 110°C, and most preferably in the range of from about 70°C to about 95°C.
• the reactor utilized in the present invention is capable and the process of the invention is producing greater than 500 lbs of polymer per hour (227 Kg/hr) to about 200,000 lbs/hr (90,900 Kg/hr) or higher of polymer, preferably greater than 1000 lbs/hr (455 Kg/hr), more preferably greater than 10,000 lbs/hr (4540 Kg/hr), even more preferably greater than 25,000 lbs/hr (1 1,300 Kg/hr), still more preferably greater than 35,000 lbs/hr (15,900 Kg/hr), still even more preferably greater than 50,000 lbs/hr (22,700 Kg/hr) and most preferably greater than 65,000 lbs/hr (29,000 Kg/hr) to greater than 100,000 lbs/hr (45,500 Kg/hr).
• a slurry polymerization process generally uses pressures in the range of from about 1 to about 50 atmospheres and even greater and temperatures in the range of 0 0 C to about 120°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, preferably a branched alkane.
• the medium employed should be liquid under the conditions of polymerization and relatively inert.
• a propane medium When used the process must be operated above the reaction diluent critical temperature and pressure.
• a hexene or an isobutene medium is employed.
• a preferred polymerization technique of an embodiment of the invention is referred to as a particle form polymerization, or a slurry process where the temperature is kept below the temperature at which the polymer goes into solution.
• a particle form polymerization or a slurry process where the temperature is kept below the temperature at which the polymer goes into solution.
• the reactor used in the slurry process of the invention is capable of and the process of an embodiment of the invention is producing greater than 2000 lbs of polymer per hour (907 Kg/hr), more preferably greater than 5000 lbs/hr (2268 Kg/hr), and most preferably greater than 10,000 lbs/hr (4540 Kg/hr).
• the slurry reactor used in the process of an embodiment of the invention is producing greater than 15,000 lbs of polymer per hour (6804 Kg/hr), preferably greater than 25,000 lbs/hr (1 1,340 Kg/hr) to about 100,000 lbs/hr (45,500 Kg/hr).
• a preferred process of an embodiment of the invention is where the process, preferably a slurry or gas phase process is operated in the presence of a cyclic bridged metallocene catalyst system of an embodiment of the invention and in the absence of or essentially free of any scavengers, such as triethylaluminum, trimethylaluminum, tri-isobutylaluminum and tri-n-hexylaluminum and diethyl aluminum chloride, dibutyl zinc and the like.
• scavengers such as triethylaluminum, trimethylaluminum, tri-isobutylaluminum and tri-n-hexylaluminum and diethyl aluminum chloride, dibutyl zinc and the like.
• This preferred process is described in WO 96/08520 and U.S. Patent No. 5,712,352 and 5,763,543.
• the process is operated by introducing a benzyl compound into the reactor and/or contacting a benz
• Polymers of the instant invention may have enhanced optical and shrinkage properties, as discussed further below.
• the polymers produced by a process of an embodiment of the invention can be used in a wide variety of products and end-use applications.
• the polymers produced include linear low-density polyethylene, plastomers, high-density polyethylenes, low-density polyethylenes, polypropylene and polypropylene copolymers.
• the polymers may be made up of, at least partially, butene, ethylene, and other olefin monomers having from 2 to 20 carbon atoms.
• the polymers may be copolymers of butene and ethylene, or terpolymers of butene, ethylene, and other olefin monomer.
• the polymers typically ethylene based polymers, have a density in the range of from 0.90 g/cc to 0.97 g/cc, preferably in the range of from 0.90 g/cc to 0.965 g/cc, more preferably in the range of from 0.90 g/cc to 0.96 g/cc, even more preferably in the range of from 0.905 g/cc to 0.95 g/cc, yet even more preferably in the range from 0.910 g/cc to 0.945 g/cc, and most preferably greater than 0.915 g/cc to about 0.935 g/cc.
• melt strength of the polymers produced using the catalyst of an embodiment of the invention are preferably greater than 4 cN, preferably greater than 5 cN and, preferably less than 10 cN.
• melt strength is measured with a capillary rheometer (RHEO-TESTERTM 1000, Goettfert, Rock Hill, SC) in conjunction with the Goettfert Rheotens melt strength apparatus (RHEOTENSTM 71.97).
• RHEOTENSTM 71.97 Goettfert Rheotens melt strength apparatus
• the take-up speed is increased at a constant acceleration of 12 mm/sec 2 , which is controlled by the WinRHEOTM program provided by Goettfert.
• the maximum pulling force (in the unit of cN) achieved before the strand breaks or starts to show draw-resonance is determined as the melt strength.
• the temperature of the rheometer is set at 190°C.
• the barrel has a diameter of 12 mm.
• the capillary die has a length of 30 mm and a diameter of 2 mm.
• the polymer melt is extruded from the die at a piston speed of 0.49 mm/sec.
• the apparent shear rate for the melt in the die is, therefore, 70 sec '1 and the speed at die exit is 17.5 mm/sec.
• the distance between the die exit and the wheel contact point should be 125 mm.
• Polymers of embodiments of the instant invention have a combination of exceptionally high shear thinning for extrusion, outstanding film optical property and excellent shrink performance.
• HD-LDPE is the only product family having most of these attributes.
• clarity of HP-LDPE is far inferior to polymers of embodiments of the instant invention.
• Conventional ZN- LLDPE are lacking of most of these attributes.
• Some easy process (i.e., very broad MWD) products from gas phase and/or slurry processes are typically very poor in optical properties.
• the shrink property of these conventional products is also somewhat insufficient for shrink application.
• polymers of embodiments of the instant invention exhibited strain-hardening behavior under the transient uniaxial extensional flow, similar to HP-LDPE.
• polymers of embodiments of the instant invention have broad MFR (over 100), which is an indicator of good processability.
• the films from these products have TD shrinkage comparable to or better than HP-LDPE, optical properties similar to HP-LDPE.
• a gas phase reactor also has the added benefit of lower cost and, in general, higher capacity.
• RETRAMAT shrink test used herein is based on NFT 54-125 and
• the ASTM method covers the determination of the plastic shrink tension and related shrink characteristics shrink force and orientation release stress of heat-shrinkable film of less than 800 ⁇ m thickness, while the specimen is totally restrained from shrinking as it is heated.
• the NFT 54-125 method covers the total shrinking process, being both the plastic and the thermal shrink process.
• the method used herein consists of exposing two film samples to a given temperature, during a given time, and to cool them down at room temperature, simulating what happens inside a shrinkage installation.
• a minimum of 10 strips of ⁇ 150 mm length and 15 mm width are prepared for both MD and TD on a sample cutter.
• Retramat stickers are applied onto the sample edges so that the shrink area of the test specimen measures exactly 100 mm in length.
• the oven temperature is 190°C and the closing duration is 45 seconds.
• one of the samples is connected to a force transducer, while the other is connected to a displacement transducer.
• a thermocouple allows following up the temperature at a few millimetres from the middle of the sample.
• the 3 parameters force - displacement - temperature
• the polymers produced by the process of an embodiment of the invention may have a molecular weight distribution, a weight average molecular weight to number average molecular weight (M w /M n ) of greater than 1.5 to about 15, particularly greater than 2 to about 10, more preferably greater than about 2.5 to less than about 8, and most preferably from 3.0 to 8.
• M w /M n weight average molecular weight to number average molecular weight
• the polymers of the present invention in one embodiment have a melt index (MI) or (I 2 ) as measured by ASTM-D-1238-E in the range from 0.01 dg/min to 1000 dg/min, more preferably from about 0.01 dg/min to about 100 dg/min, even more preferably from about 0.01 dg/min to about 50 dg/min, even more preferably from about 0.01 dg/min to about 10 dg/min, and most preferably from about 0.05 dg/min to about 10 dg/min.
• MI melt index
• I 2 melt index
• the polymers of the invention in an embodiment have a melt index ratio (I21/I2) (I2 is measured by ASTM-D-1238-F) equal to or greater than 49.01 1 x MI (" 04304 ⁇ ; more preferably equal to or greater than 57.18 x MI ⁇ "0 - 4304) ; as shown in Figure 3.
• I21/I2 melt index ratio
• the polymers as described herein may have a narrow composition distribution characterized in that the T75-T25 value is lower than 25, preferably lower than 20, more preferably lower than 15, and most preferably lower than 10, wherein T25 is the temperature at which 25% of the eluted polymer is obtained and T75 is the temperature at which 75% of the eluted polymer is obtained in a TREF experiment as described herein.
• the TREF-LS data reported herein were measured using an analytical size TREF instrument (Polymerchar, Spain), with a column of the following dimension: inner diameter (ID) 7.8 mm and outer diameter (OD) 9.53 mm and a column length of 150 mm. The column was filled with steel beads.
• the polymers of an embodiment of the invention may be blended and/or coextruded with any other polymer.
• Non-limiting examples of other polymers include linear low density polyethylenes produced via conventional Ziegler-Natta and/or metallocene catalysis, elastomers, plastomers, high pressure low density polyethylene, high density polyethylenes, polypropylenes and the like.
• Polymers produced by the process of an embodiment of the invention and blends thereof are useful in such forming operations as film, sheet, and fiber extrusion and co-extrusion as well as blow molding, injection molding and rotary molding.
• Films include blown or cast films formed by monolayer extrusion, coextrusion or by lamination useful as shrink sleeves, shrink wrap, bundle shrink, cling film, stretch film, sealing films, oriented films, snack packaging, heavy duty bags, grocery sacks, baked and. frozen food packaging, medical packaging, industrial liners, membranes, etc. in food-contact and non-food contact applications.
• Fibers include melt spinning, solution spinning and melt blown fiber operations for use in woven or non-woven form to make filters, diaper fabrics, medical garments, geotextiles, etc.
• Extruded articles include medical tubing, wire and cable coatings, geomembranes, and pond liners. Molded articles include single and multi-layered constructions in the form of bottles, tanks, large hollow articles, rigid food containers and toys, etc.
• the methylaluminoxane (MAO) used was a 30 weight percent MAO solution in toluene (typically 13.5 wt % Aluminum and 28.2 wt % MAO by NMR) available from Albemarle Corporation (Baton Rouge, LA). Davison 948 silica dehydrated to 600 0 C (silica gel) was used and is available from W.R. Grace, Davison Chemical Division (Baltimore, MD). Anhydrous, oxygen- free solvents were used. The synthesis of (CH 2 ) 4 Si(C 5 Me4(CH 2 )4Si(C 5 Me 4 )(C 5 H5)ZrCl 2 is described in U.S. Patent No. 6,388,155.
• Crosfield ES757 silica (741 g) (INEOS Silicas Limited, Warrington, U.K.), dehydrated at 600 °C, was added to a stirred (overhead mechanical conical stirrer) mixture of toluene (2 L) and 30 wt% solution of methyl aluminoxane in toluene (874 g, 4.52 mol).
• the silica was chased with toluene (200 mL) then the mixture was heated to 90 °C for 3 h. Afterwards, volatiles were removed by application of vacuum and mild heat (40°C) overnight then the solid was allowed to cool to room temperature.
• the silica was chased with toluene (200 mL) then the mixture was heated to 90 °C for 3 h. Afterwards, volatiles were removed by application of vacuum and mild heat (40 °C) overnight, then the solid was allowed to cool to room temperature.
• silica (741 g), dehydrated at 600°C, was added to a stirred (overhead mechanical conical stirrer) mixture of toluene (2 L) and 30 wt% solution of methyl aluminoxane in toluene (874 g, 4.52 mol).
• the silica was chased with toluene (200 mL) then the mixture was heated to 9O 0 C for 3 h. Afterwards, volatiles were removed by application of vacuum and mild heat (40 0 C) overnight then the solid was allowed to cool to room temperature.
• the polymers of Examples 1 and 2 were prepared from ethylene and butene-1 monomers in a pilot-scale continuous gas phase fluidized bed reactor using CAT A.
• the reactor was operated at 70°C and 170 psi ethylene partial pressure.
• the fluidized bed was made up of polymer granules and the average bed weight was approximately 100 to 170 lbs.
• aluminum distearate was added to the reactor as a 20 wt % slurry in mineral oil at concentrations on a resin basis from 6 and 17 ppmw (parts per million weight).
• the conditions for making polymers of Examples 1 and 2 are listed in Table 3.
• the reactor granules of Examples 1 and 2 were dry blended with additives before being compounded on a 2.5" Davis-Standard single-screw extruder equipped with mixing pins and underwater pelletizer at an output rate was approximately 100 lb/hr.
• the compounded pellets of examples 1 and 2 were then film extruded on a 2.5" Gloucester line with a 6" oscillating die and an air ring from Future Design Inc. (Mississauga, Ontario, Canada).
• the output rate was about 150 lbs/hr (8 lbs/hr-in die circumference) and the die gap was 45 mils.
• Film gauge was 1 mil and blow up ratio (BUR) varied from 2.5 to 3.5.
• the die temperature was typically 20 to 24".
• the die temperature was about 199 0 C (390 0 F).
• Table 4 compares the properties of the polymers of Examples 1 and 2 to the properties of the following reference polymers: Borealis Borstar FB2230 (Borealis A/S, Vienna, Austria). Dow DNDA7340 (The Dow Chemical Company, Midland, MI). Dow DYNH-I (The Dow Chemical Company, Midland, MI). ExxonMobil LDl 03.09 (from Exxon Mobil Chemical Company, Houston, TX). The films of reference were made under similar conditions on the same film line. Table 4: Properties of Polymers of Examples 1 and 2 and Reference Polymers
• a polymer of an embodiment of the invention can improve the optical properties of other LLDPE polymers when it is blended in 5 as a minor component.
• a polymer of an embodiment of this invention was blended in at 10% (by weight) of the final product using an on-line blending set-up on a Battenfeld Gloucester (Gloucester, MA ) film line. In this set-up, the blend components were weighted separately according to the blend ratio and added to a mixing chamber, where the components were mixed by
• the line was equipped with a 2.5" single screw extruder, a 6" oscillating die and an air ring from Future Design Inc. (Mississauga, Ontario, Canada).
• the output rate was 151 lbs/hr (8 lbs/hr-in dir circumference) and the die gap was 45 mil.
• Film gauge was 1 mil and BUR was held constant at 2.5. FLH was typically 20 to 24".
• LDPE LDPE to improve optical properties
• the loss in toughness is dramatic.
• blending such polymers also improves the extrusion performance of the base polymers, as indicated by the increase in the specific output (lbs/hp-hr), making the extrusion process more energy efficient.
• the extensional viscosity of a polymer increases with strain rate.
• the transient uniaxial extensional viscosity of a linear polymer can be predicted as is known to those skilled in the art. Strain hardening occurs when the polymer is subjected uniaxial extension and the transient extensional viscosity increases more than what is predicted from linear viscoelastic theory.
• Figures 1 and 2 show strain hardening at 150 0 C of ethylene/hexene copolymers of an embodiment of the instant invention prepared using a lab-scale gas phase reactor and CAT C as a catalyst (Example 5 and Figure 2). This is compared to ExxonMobil LD 103.09 (from ExxonMobil Chemical Company, Houston, TX) ( Figure 1). The samples were compounded on a Haake Polylab system (Thermo Fisher Scientific, Inc., Waltham, MA) and blown into films on a Haake-Brabender combination system (Thermo Fisher Scientific, Inc., Waltham, MA).
• Fig. 3 is a graph of MFR v. MI for polymers of embodiments of the instant invention (using (C 4 H 8 )Si(CsMe 4 )(CsH 4 )ZrMe 2 as the catalyst) and comparative polymers.
• polymers of embodiments of the instant invention satisfy the following relations: MFR > (49.01 1 x MI (' ° 4304) ) and MFR > (57.18 x MI (043(M) .
• Fig. 4 is a graph of Retramat shrinkage v. MD Plastic Force for films made from polymers of embodiments of the instant invention (using (C 4 H 8 )Si(C 5 Me 4 )(C 5 H 4 )ZrMe 2 as the catalyst) including Examples 1 and 2, and comparative films.
• the films of embodiments of the instant invention generally have an area Retromat shrinkage of greater than 60% and an MD plastic tension of less than about 0.08 MPa.
• Fig. 5 is a graph of g' v. molecular weight for polymers of embodiments of the instant invention (using (C 4 H 8 )Si(C 5 Me 4 )(C 5 H 4 )ZrMe 2 as the catalyst) and comparative polymers.
• polymers of embodiments of the instant invention satisfy the following relations: 0.5 ⁇ g' avg ⁇ 0.9 and M w /M n ⁇ 4.6.
• 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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