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    • 专利摘要:
    NON-WOVEN CLOTH, CONTINUOUS SPINNING NON-WOVEN CLOTH LAMINATE STRUCTURE, MULTILAYER STRUCTURE, ETHYLENE-BASED POLYMER COMPOSITION AND FIBER OR FABRIC The present invention provides non-wovens or staple fibers or binders prepared with an ethylene-based polymer having a Comonomer Distribution Constant in the range of greater than 100 to 400, a vinyl unsaturation of less than 0.1 vinyl per thousand carbon atoms present in the backbone of the ethylene-based polymer composition; a zero shear viscosity ratio (ZSVR) in the range of 1 to less than 2; a density in the range of 0.930 to 0.970 g/cm3, a melt index (I2) in the range of 15 to 30 or 10 to 50g/10 minutes, a molecular weight distribution (Mw/Mn) in the range of 2 to 3 .5, and a molecular weight distribution (Mz/Mw) in the range less than 2.
    公开号:BR112014008019B1
    申请号:R112014008019-4
    申请日:2012-10-04
    公开日:2021-08-03
    发明作者:Mehmet Demirors；Selim Bensason；Jacquelyn A. Degroot；Gert J. Claasen；Thor Gudmundsson；Jason C. Brodil
    申请人:Dow Global Technologies Llc；
    IPC主号:
    专利说明:

    technical field
    [001] The present invention relates to continuous spinning non-woven fabrics. Invention History
    [002] Continuous spinning nonwovens are widely used in various end use applications such as hygiene, medical, industrial or automotive to provide low basis weight, economical, tough and cloth-like fabrics. Continuous spinning nonwovens typically comprise single-component or bi-component fibers. Monocomponent fibers include, for example, the configuration of islands in the sea in a segmented pie, side by side containing core/sheath and the like. A common bicomponent fiber configuration is a core/sheath structure, where the core comprises polypropylene homopolymer and the sheath comprises polyethylene. The core-sheath provides stretchability, spin stability, heat resistance, modulus, ultimate tensile strength inherent in polypropylene, while providing the additional characteristic of soft feel, lower bonding temperatures, and greater elongation attributed to the addition of polyethylene sheath. Although two-component structures, such as the sheath/core type, have been gaining in popularity, especially in medical and healthcare applications where consumers demand a soft touch and improved fit in items such as feminine care products, diapers, pants, training, adult incontinence items, as well as drapes and robes for surgical purposes. However, the drawbacks of bicomponent fibers involve high cost to purchase and install a bicomponent line versus a monocomponent line, the increased complexity of using multiple resins, the reduced ability to incorporate recyclable edges from fabrics due to the inability of polyethylene and polypropylene and reduced productivity.
    [003] Consequently, there is a need to improve the softness of continuous spinning non-woven fabrics comprising single-component fibers while maintaining other key performance attributes such as fabric strength and processability. Invention Summary
    [004] The present invention provides continuous spinning nonwovens. Continuous spin nonwovens in accordance with the present invention comprise single-component fibers prepared with an ethylene-based polymer composition comprising: (a) an amount equal to or less than 100 percent by weight of the ethylene-derived units ; and (b) an amount less than 30 percent by weight of units derived from one or more α-olefin comonomers; being that said ethylene-based polymer composition is characterized by having a Comonomer Distribution Constant in the range of more than 100 to 400, a vinyl unsaturation of less than 0.1 vinyl per thousand carbon atoms present in the main chain of the composition of ethylene-based polymer; a zero shear viscosity ratio (ZSVR) in the range of 1 to less than 2; a density in the range of 0.930 to 0.970 g/cm3, a melt index (I2) in the range of 15 to 30 g/10 minutes, a molecular weight distribution (Mw/Mn) in the range of 2 to 3.5, and a molecular weight distribution (Mz/Mn) in the range of less than 2. Detailed Description of the Invention
    [005] The present invention provides continuous spinning nonwovens. Continuous spin nonwovens in accordance with the present invention comprise single-component fibers prepared with an ethylene-based polymer composition comprising: (a) an amount equal to or less than 100 percent by weight of the ethylene-derived units; and (b) less than 30 percent by weight of units derived from one or more α-olefin comonomers; being that said ethylene-based polymer composition is characterized by having a Comonomer Distribution Constant in the range of more than 100 to 400, a vinyl unsaturation less than 0.1 vinyl per thousand carbon atoms, present in the main chain of the composition of ethylene-based polymer; a zero shear viscosity ratio (ZSVR) in the range of 1 to less than 2; a density in the range of 0.930 to 0.970 g/cm3, a melt index (I2) in the range of 15 to 30g/10 minutes, a molecular weight distribution (Mw/Mn) in the range of 2 to 3.5, and a molecular weight distribution (Mz/Mn) in the range of less than 2.
    [006] The present invention further provides staple fibers or binders obtained through continuous filament spinning prepared with an ethylene-based polymer composition comprising: (a) an amount equal to or less than 100 percent by weight of the ethylene-derived units ; and (b) less than 30 percent by weight of units derived from one or more α-olefin comonomers; being that said ethylene-based polymer composition is characterized by having a Comonomer Distribution Constant in the range of more than 100 to 400, a vinyl unsaturation less than 0.1 vinyl per thousand carbon atoms, present in the main chain of the composition of ethylene-based polymer; a zero shear viscosity ratio (ZSVR) in the range of 1 to less than 2; a density in the range of 0.930 to 0.970 g/cm3, a melt index (I2) in the range of 10 to 50g/10 minutes, a molecular weight distribution (Mw/Mn) in the range of 2 to 3.5, and a molecular weight distribution (Mz/Mn) in the range of less than 2.
    [007] The ethylene-based polymer composition comprises (a) an amount equal to or less than 100 percent, for example, at least 70 percent, or at least 80 percent, or at least 90 percent in weight of ethylene-derived units; and (b) less than 30 percent, for example, less than 25 percent, or less than 20 percent, or less than 10 percent by weight of units derived from one or more α-olefin comonomers. The term "ethylene-based polymer composition" refers to a polymer that contains more than 50 mole percent polymerized ethylene monomer (based on the total amount of polymerizable monomers) and optionally may contain at least one comonomer .
    [008] α-Olefin comonomers typically have no more than 20 carbon atoms. For example, α-olefin comonomers can preferably have from 3 to 10 carbon atoms, and more preferably from 3 to 8 carbon atoms. Representative α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1- pentene. The one or more α-olefin comonomers may, for example, be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene; or alternatively, from the group consisting of 1-hexene and 1-octene.
    [009] The ethylene-based polymer composition is characterized by having a Comonomer Distribution Constant in the range of more than 100 to 400, for example, from 100 to 300, or from 100 to 200.
    [010] The ethylene-based polymer composition is characterized by having a zero shear viscosity ratio (ZSVR) in the range of 1 to less than 2, for example, from 1 to 1.9, or from 1 to 1, 8 or from 1 to 1.7.
    [011] The ethylene-based polymer composition has a density in the range of 0.930 to 0.970 g/cm3. For example, density can range from a lower limit of 0.930 to 0.935, or from 0.940 g/cm3 to an upper limit of 0.935, 0.940, 0.945, 0.950, 0.960, 0.965 or 0.970 g/cm3.
    [012] The ethylene-based polymer composition has a molecular weight distribution (Mw/Mz) in the range of 2 to 3.5. For example, the molecular weight distribution (Mw/Mn) can range from a lower limit of 2, 2.1 or 2.2, to an upper limit of 2.5, 2.7, 2.9, 3 .0, 3.2 or 3.5.
    [013] Regarding continuous spinning non-woven fabrics comprising single-component fibers, the ethylene-based polymer composition has a melt index (I2) in the range of 15 to 30g/10 minutes. For example, the melt index (I2) can range from a minimum limit of 15, 16, 17, 18 or 20g/10 minutes to a maximum limit of 18, 20, 24, 26, 28 or 30g/10 minutes .
    [014] Regarding the spinning of continuous filaments for binder fibers or staple fibers, the ethylene-based polymer composition has a melt index (I2) in the range of 10 to 50g/10 minutes. For example, the melt index (I2) can range from a lower limit of 10, 12, 15, 16, 17, 18 or 20g/10 minutes to an upper limit of 18, 20, 24, 26, 28, 30, 40, 45 or 50g/10 minutes.
    [015] The ethylene-based polymer composition has a molecular weight (Mw) in the range of 15,000 to 150,000 daltons. For example, the molecular weight (Mw) can range from a lower limit of 15,000 to 20,000, or 30,000 daltons, to an upper limit of 100,000, 120,000, or 150,000 daltons.
    [016] The ethylene-based polymer composition has a molecular weight distribution (Mz/Mw) in the range of less than 3, for example, less than 2, or from 1 to 2.
    [017] The ethylene-based polymer composition has a vinyl unsaturation less than 0.1 vinyls per thousand carbon atoms present in the backbone of the ethylene-based polymer composition. For example, vinyl unsaturation less than 0.08, less than 0.06, less than 0.04, less than 0.02, less than 0.01 or less than 0.001 vinyls per thousand carbon atoms present in the main chain of ethylene-based polymer composition.
    [018] In one embodiment, the ethylene-based polymer composition comprises an amount equal to or less than 100 parts, for example, less than 10 parts, less than 8 parts, less than 5 parts, less than 4 parts, less than 1 part, less than 0.5 part, or less than 0.1 part by weight of hafnium residues remaining from a hafnium-based metallocene catalyst per one million parts of polyethylene composition. Hafnium residues remaining from the hafnium-based metallocene catalyst in the ethylene-based polymer composition can be measured using X-ray fluorescence (XRF) calibrated to reference standards. Polymeric resin beads can be compression molded at elevated temperature into plates having a thickness of about 3/8 of an inch for X-ray measurement in a preferred method. At very low metal concentrations, such as less than 0.1 ppm, ICP-AES would be a suitable method to determine metallic residues present in the ethylene-based polymer composition.
    [019] In another embodiment, the ethylene-based polymer composition comprises an amount equal to or less than 100 parts, for example, less than 10 parts, less than 8 parts, less than 5 parts, less than 4 parts, less than 1 part, less than 0.5 part, or less than 0.1 part by weight of metal complex residues, remaining from a catalytic system comprising a metal complex of a polyvalent aryloxyether per one million parts of ethylene-based polymer composition . Remaining metal complex residues from the catalytic system comprising a metal complex of a polyvalent aryloxyether in the ethylene-based polymer composition can be measured by X-ray fluorescence (XRF), which is calibrated against reference standards. Polymeric resin beads can be compression molded at elevated temperature into plates having a thickness of about 3/8 inch for X-ray measurement in a preferred method. At very low metal complex concentrations, such as less than 0.1 ppm, ICP-AES would be a suitable method to determine metal complex residues present in the ethylene-based polymer composition.
    [020] The ethylene-based polymer composition may comprise additional components such as one or more other polymers and/or additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, fillers/fillers, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, antiblockers, slip agents, tackifiers, retardants flame retardants, antimicrobial agents, odor reducing agents, antifungal agents, and combinations thereof. The ethylene-based polymer composition can contain from about 0.1 to about 10 percent combined by weight of such additives, based on the weight of the ethylene-based polymer composition, including such additives.
    [021] In one embodiment, the ethylene-based polymer composition has a comonomer distribution profile comprising a monomodal or bimodal distribution in the temperature range of 35°C to 120°C, excluding purge.
    [022] Any conventional ethylene (co)polymerization reaction processes can be employed to produce the ethylene-based polymer composition. Such conventional ethylene (co)polymerization reaction processes include, but are not restricted to gas phase polymerization process, slurry phase polymerization process, solution phase polymerization process, and combinations thereof, using one or more reactors conventional ones, for example, fluidized bed gas phase reactors, loop reactors, stirred tank reactors, batch reactors in parallel, series, and/or any combination thereof.
    [023] In a first embodiment, the ethylene-based polymer is prepared via a process comprising the steps of: (a) polymerizing ethylene and optionally one or more α-olefins in the presence of a first catalyst to form a semi-crystalline polymer based of ethylene, in a first reactor or the first part of a multi-part reactor; and (b) reacting freshly supplied ethylene and optionally one or more α-olefins, in the presence of a second catalyst comprising an organometallic catalyst, thereby forming an ethylene-based polymer composition in at least one other reactor or the last part of a multi-part reactor, where at least one of the catalytic systems in step (a) or (b) comprises a metal complex of a polyvalent aryloxyether corresponding to the formula:
    where M3 is Ti, Hf or Zr, preferably Zr.
    [024] Ar4 is independently at each occurrence a substituted C9-20 aryl group, where the substituents, independently at each occurrence, are selected from the group consisting of alkyl groups; cycloalkyl; and aryl; and halo, trihydrocarbylsilyl and halohydrocarbyl substituted derivatives thereof, provided that at least one substituent is devoid of coplanarity with the aryl group to which it is attached;
    [025] T4 is, independently at each occurrence, a C2-20 alkylene, cycloalkylene or cycloalkenylene group, or an inertly substituted derivative thereof;
    [026] R21 is, independently at each occurrence, hydrogen, halo group, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or di(hydrocarbyl)amino with up to 50 atoms not counting hydrogen;
    [027] R3 is, independently in each occurrence, hydrogen, halo, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or amino with up to 50 atoms not counting hydrogen, or two R3 groups on the same arylene ring together or a group R3 and R21 in the same or on a different arylene ring together form a divalent linking group attached to the arylene group at two positions or join two different arylene rings; and
    [028] RD is, independently in each occurrence, halo or hydrocarbyl or trihydrocarbylsilyl group with up to 20 atoms not containing hydrogen, or 2 RD groups together are a hydrocarbylene, hydrocarbadiyl, diene, or poly(hydrocarbyl)silylene group.
    [029] The ethylene-based polymer composition can be produced via solution polymerization, according to the representative process below.
    [030] All raw materials (ethylene, 1-octene) and the process solvent (a high-purity isoparaffinic solvent with a narrow boiling range, marketed under the brand name Isopar E by ExxnonMobil Corporation) are purified with molecular sieves before introduction in a reaction environment. Hydrogen is supplied in pressurized cylinders with a high degree of purity and is not further purified. The monomer feed stream to the reactor (ethylene) is pressurized via a mechanical compressor at a pressure above the reaction pressure, close to 750 psig. The supply of solvent and comonomer (1-octene) is pressurized via a positive mechanical displacement pump at a pressure above the reaction pressure, approximately 750 psig. The individual catalytic components are manually batch diluted to specified component concentrations with purified solvent (Isopar E) and pressurized at a pressure above reaction pressure, approximately 750 psig. All reaction feed streams are measured with independently controlled mass flow meters with automated computerized valve control systems.
    [031] The continuous solution polymerization reactor system, according to the present invention, consists of two loops filled with liquid, non-adiabatic, isothermal, circulating and independently controlled. Each reactor has independent control of all fresh feeds of solvent, monomer, comonomer, hydrogen and catalyst component. The combined solvent, monomer, comonomer and hydrogen feed to each reactor is temperature controlled in a range between 5oC to 50oC and typically 40oC passing through the feed stream through a heat exchanger. Fresh monomer feed to polymerization reactors can be manually aligned to add comonomer to one of the following three options: the first reactor, second reactor or common solvent and then partition between two reactors in proportion to the split of the solvent feed . The total fresh feed for each polymerization reactor is injected into the reactor at two sites with approximately equal reactor volumes between each injection site. Fresh feed is typically controlled with each injector receiving half the mass flow of the total fresh feed. The catalyst components are injected into the polymerization reactor through specially designed injection devices, and are each separately injected in the same relative location in the reactor with no contact time before the reactor. The primary catalyst component feed is computer controlled to keep the reactor monomer concentration within a specified target. The two cocatalyst components are fed based on specified molar ratios calculated for the primary catalyst component. Immediately after each fresh injection site (either feed or catalyst), feed streams are mixed with the contents of the circulating polymerization reactor with static mixing elements. The contents of each reactor are continuously circulated through heat exchangers responsible for removing most of the reaction heat and with the coolant side temperature being responsible for maintaining the isothermal reaction environment at the specified temperature. Circulation around each reactor loop is provided by a spiral pump. The effluent from the first polymerization reactor (containing solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) leaves the first reactor loop, passing through a control valve (responsible for maintaining the pressure of the first reactor within a target specified) and is injected into the second polymerization reactor of similar design. As the current egresses from the reactor, it is contacted with a deactivating agent, eg water, to stop the reaction. Also, various additives, such as antioxidants, can be added at this time. The stream then proceeds to another set of static mixing elements to uniformly disperse the catalytic deactivating agent and additives.
    [032] After addition of the additive, the effluent (containing solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) passes through a heat exchanger to raise the temperature of the stream in preparation to separate the polymer from the other reaction components with lower boiling points. The stream then enters a two-stage separation and devolatization system where the polymer is removed from the solvent, hydrogen and unreacted monomer and comonomer. The recycled stream is purified before re-entering the reactor. The separated, devolatized polymeric melt is pumped through a specially designed matrix for submerged pelletizing, cut into solid, uniform pellets, dried and transferred to a hopper/hopper.
    [033] In a second embodiment, the ethylene-based polymer is prepared via gas phase polymerization process, as described below. The gas phase polymerization can be conducted in a single reactor, for example a gas phase fluidized bed reactor.
    [034] In production, the hafnium-based metallocene catalytic system, as described below, including a cocatalyst, ethylene, optionally one or more alpha-olefin comonomers, hydrogen, optionally one or more inert gases and/or liquids, for example , N 2 , isopentane, and hexane and optionally one or more continuity additives, for example ethoxylated stearyl amine or aluminum distearate or combinations thereof, are continuously fed to a reactor, for example a fluidized bed gas phase reactor. The reactor is in fluid communication with one or more discharge tanks, surge tank, purge tanks, and/or recycle compressors. The temperature in the reactor is typically in the range from 70 to 115°C, preferably from 75 to 110°C, more preferably from 75 to 100°C and the pressure is in the range from 15 to 30 atm, preferably from 17 to 26 atom. A distributor plate at the bottom of the polymer bed provides a uniform upstream flow of monomer, comonomer and inert gases. A mechanical stirrer can also be provided to facilitate contact between the solid particles and the comonomer gas stream. A vertical cylindrical fluidized bed reactor can be bulb-shaped at the top to facilitate gas velocity reduction; thus, it allows the granular polymer to separate from the upward flowing gases. The unreacted gases are then cooled to remove heat of polymerization, recompressed, and then recycled to the bottom of the reactor. After the resin is removed from the reactor, it is transported to a purge box to purge residual hydrocarbons. Moisture can be introduced to react with catalyst and residual cocatalyst prior to exposure and reaction with oxygen. The inventive polyethylene composition can then be transferred to an extruder to be pelletized. Such pelleting techniques are generally known. The polyethylene composition of the invention can also be melt filtered. After the melting process in the extruder, the molten composition is passed through one or more sieves/active filters, positioned in series of more than one, with each sieve/active filter having a micron retention size of about 2μm to about 400μ m (2 to 4 x 10-5m), and preferably from about 2μm to about 300μm (2 to 3 x 10-5) and most preferably from about 2μm to about 70μm (2 to 7x10 -6m), at a mass flow of about 5 to about 100 lb/hr/square inch (1.0 to about 20 kg/m2). Such additional melt filtering is described in U.S. Patent No. 6,485,662, incorporated herein by reference as it describes melt filtering.
    [035] The hafnium-based catalytic system, as used herein, refers to a catalyst composition, capable of catalyzing the polymerization of ethylene monomers and optionally one or more α-olefin comonomers to produce polyethylene. In addition, the hafnium-based catalytic system comprises a hafnocene component. The hafnocene component has an average particle size in the range of 12 to 35 µm; for example, the hafnocene component has an average particle size in the range of 20 to 30 µ m, for example 25 µ . The hafnocene component comprises hafnium complexes of the mono-, bis- or tris-cyclopentadienyl type. In one embodiment, the cyclopentadienyl type linker comprises cyclopentadienyl or isolobal to cyclopentadienyl linkers and their substituted versions. Representative examples of isolobal to cyclopentadienyl linkers include, but are not limited to, cyclopentaphenantrenyl, indenyl, benzindenyl, fluorenyl, octahydrofluorenyl, cyclooctatetraenyl, cyclopentacyclododecene, phenantrindenyl, 3,4-benzofluorenyl, 9-phenylfluorenyl, cyclopentyl[8-H] 7H-dibenzofluorenyl, indeno[1,2-9]anthrene, thiophenoindenyl, thiophenofluorenyl, their hydrogenated versions (eg 4,5,6,7-tetrahydroindenyl, or “H4Ind”) and their substituted versions. In one embodiment, the hafnocene component is an unbridged bis-cyclopentadienyl hafnocene and its substituted versions. In another embodiment, the haphnocene component excludes the unsubstituted unsubstituted bis-cyclopentadienyl haphnocenes, and the bonded and unbridged bis-indenyl haphnocenes and the unbridged bis-indenyl haphnocenes. The term "unsubstituted", as used herein with respect to the hafnium-based catalytic system, means that there are only hydride groups attached to the rings and no other groups. Preferably, the hafnocene useful in the present invention can be represented by the formula (where "Hf" is hafnium): CpnHfXp where n is 1 or 2, p is 1, 2, or 3, each Cp is independently a cyclopentadienyl linker or isolobal linker a cyclopentadienyl or a substituted version thereof bound to hafnium; and X is selected from the group consisting of hydride, halides, C1 to C10 alkyls and C2 to C12 alkenyls; and where when n is 2, each Cp may be linked to another group through a bridged A group selected from the group consisting of C1 to C5 alkylenes, oxygen, alkylamine, silyl hydrocarbons, and siloxyl hydrocarbons. An example of C1 to C5 alkylenes include bridged ethylene(--CH2CH2--) groups; an example of a bridged alkylamine group includes methylamide(--CH3)N--); an example of a bridged silyl-hydrocarbon group includes dimethylsilyl(--CH3)2Si--); and an example of a bridged siloxyl hydrocarbon group includes (—O—(CH 3 ) 2 Si—O—). In a specific embodiment, the hafnocene component is represented by formula (1), where n is 2 and p is 1 or 2.
    [036] As used herein, with respect to the hafnium-based catalytic system, the term "substituted" means that the referred group has at least one moiety in place of one or more hydrogens at any position, the moieties being selected from groups such as halogen radicals such as F, Cl, Br, hydroxyl groups, carbonyl groups, carboxy groups, amine groups, phosphine groups, alkoxy groups, phenyl groups, naphthyl groups, C1 to C10 alkyl groups, C2 to C10 alkenyl groups, and their combinations. Examples of substituted alkyls and aryls include, but are not restricted to acyl radicals, alkylamino radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbamoyl radicals, alkyl and dialkyl carbamoyl radicals, acyloxy radicals, acylamino radicals, arylamino radicals, and combinations thereof. More preferably, the hafnocene component useful in the present invention can be represented by the formula: (CpR5)2HfX2 where each Cp is a cyclopentadienyl linker and each is linked to hafnium; each R is independently selected from hydrides and C1 to C10 alkyls, most preferably hydrides and C1 to C5 alkyls; and X is selected from the group consisting of hydride, halide, C1 to C10 alkyls and C2 to C12 alkenyls, and more preferably X is selected from the group consisting of halides, C2 to C6 alkylenes and C1 to C6 alkyls, and most preferably X is selected from the group consisting of chloride, fluoride, C1 to C5 alkyls and C2 to C6 alkylenes. In a more preferred embodiment, hafnocene is represented by the formula: (CpR5)2HfX2 wherein at least one R group is an alkyl as defined above, preferably a C1 to C5 alkyl and the others are hydrides. In a more preferred embodiment, each Cp is independently substituted with one, two or three groups selected from the group consisting of methyl, ethyl, propyl, butyl, and their isomers.
    [037] In one embodiment, the hafnocene-based catalytic system is heterogeneous, that is, the hafnocene-based catalyst may also comprise a support material. The support material can be any material known in the art to support catalyst compositions; for example an inorganic oxide; or alternatively, silica, alumina, silica-alumina, magnesium chloride, graphite, magnesia, titania, zirconia, and montmorillonite, any of which may be chemically/physically modified, such as through fluoridation, calcination or other processes known in the state of technique. In one embodiment, the support material is a silica material having an average particle size as determined by Malvern analysis, from 1 to 60 mm; or alternatively, from 10 to 40 mm.
    [038] In one embodiment, the hafnocene component may be a spray-dried hafnocene composition containing a microparticulate filler, such as Cabot TS-610.
    [039] The catalytic system based on hafnocene can also comprise an activator. Any suitable activator known to activate the catalyst components for olefin polymerization may be suitable. In one embodiment, the activator is an alumoxane; alternatively, metallumoxane, as described by J.B.P. Soares and A.E. Hamielec in 3(2) POLYMER REACTION ENGINEERING, 131-200 (1995). The alumoxane may preferably be co-supported on the support material in a molar ratio of aluminum to hafnium (Al:Hf) ranging from 80:1 to 200:1, most preferably from 90:1 to 140:1.
    [040] Such hafnium-based catalytic systems are also described in detail in US Patent No. 6,242,545 and US Patent No. 7,078,467, incorporated herein by reference.
    [041] The ethylene-based polymer composition is formed into single-component fibers via different techniques, for example, via foundry spinning. Such monocomponent fibers can be continuous filaments, or alternatively, they can be staple fibers. Continuous filaments can be crimped/crimped and then cut to produce staple fibers. Monocomponent fibers can be monoconstituents, that is, contain only the ethylene-based polymer composition; or alternatively, the monocomponent fibers can be multi-constituent, i.e. a blend of the ethylene-based polymer composition, and one or more other polymers. The one-component fiber comprising the ethylene-based polymer composition can withstand cabin pressures in the range of at least 3000 Pa, for example at least 3700 Pa, during the melt spinning step of the continuous spinning process.
    [042] In melt spinning, the ethylene-based polymer composition or a mixture of the ethylene-based polymer composition and one or more other polymers is extruded in the molten state and forced through fine holes of a metal plate called spinneret in ara or other gas, where it is cooled and solidified. The solidified filaments can be expelled via air jets, rotating cylinders or “godets”, and can be placed on a conveyor belt in the form of a blanket or wound into coils.
    [043] The nonwovens, according to the present invention, can be manufactured via different techniques. Such methods include, but are not restricted to continuous spinning processes, carded blanket process, airlaid spinning process, thermocalendering process, adhesive bonding process, hot air bonding process, needling, hydroentanglement process, electrospinning process, and their combinations.
    [044] In the continuous spinning process, the fabrication of non-wovens includes the following steps: (a) extruding filaments of ethylene-based polymer composition from a spinner; (b) rapidly cooling the filaments of the ethylene-based polymer composition with air flow, generally cooled to accelerate the solidification of the molten filaments of the ethylene-based polymer composition; (c) attenuate/soften the filaments by advancing them through the cooling zone with an extraction tension that can be applied by pneumatically dragging the filaments in an air stream or by winding them around extraction cylinders of the type commonly used in the fiber industry textiles; (d) collecting the extracted fibers in a blanket on a foraminous surface, such as a mobile screen or porous belt; and (e) bonding the loose filament mat to the non-woven fabric. Bonding can be achieved by various means, including, but not limited to, the thermocalendering process, adhesive bonding process, hot air bonding process, needling process, hydroentangling process, and combinations thereof.
    [045] The continuous spinning nonwovens, according to the present invention, have peak tensile strength in the machine direction of at least 15 N/5 cm, where said continuous spinning nonwoven is a 20GSM prepared fabric at a maximum cabin pressure of at least 3000 Pa, for example at least 3700 Pa.
    [046] Continuous spinning nonwovens can be formed in multilayer structure or laminated. Such multi-layer structures comprise at least 2 or more layers, where at least one or more layers are continuous-spun nonwovens according to the present invention, and one or more of the other layers are selected from one or more non-woven layers. fabric via melt blowing, one or more layers of non-woven fabric produced by the wet-laid process, one or more layers of non-woven fabric produced by the air-laid process , one or more mats produced by any non-woven or foundry spinning process, one or more film layers, such as cast film, blown film, one or more coating layers derived from a via coating composition, for example, extrusion coating, spray coating, gravure coating, printing, dipping, roller contacting, or blade coating. Laminated structures can be joined by any number of bonding methods; thermal bonding, adhesive lamination, hydroentanglement, needling. Structures can range from S to SX, or SXX, or SXXX or SXXXX or SXXXXX, where X can be a film, coating, or other non-woven material in any combination. Additional continuous spinning layers can be produced from the ethylene-based polymer composition, as described herein, and optionally in combination with one or more polymers and/or additives.
    [047] In the case of continuous spin fibers or binders, they can be blended with a variety of other fibers including synthetic fibers such as PE, PP, PET or natural fibers such as cellulose, rayon or cotton. These fibers can be processed through the wet method, air flow or carded into a non-woven mat. The non-woven mat can then be laminated to other materials.
    [048] Continuous spinning nonwovens can be used in a variety of end-use applications including, but not limited to, absorbent hygiene products such as diapers, feminine hygiene items, adult incontinence products, wipes, bandages and wound dressings, as well as disposable slippers and footwear, medical applications such as insulating gowns, surgical gowns, surgical drapes and shields, surgical gowns, caps/caps, masks and medical packaging. Examples
    [049] The following examples illustrate the present invention, although they are not intended to limit its scope. The examples of the present invention demonstrate that single-component fibers comprising ethylene-based polymer compositions facilitate the spinning of fine denier fibers and soft/draped continuous spin nonwovens while maintaining acceptable maximum peak tensile strength. Inventive Example Compositions 1-5
    [050] Inventive Example Compositions 1-2 and 4-5 are ethylene-octene copolymers that were prepared via solution polymerization process in a dual reactor configuration connected in series in the presence of a catalytic system comprising a metal complex of a polyvalent aryloxyether as described above. The properties of the ethylene-octene copolymer compositions of Inventive Example Compositions 1-2 and 4-5 are reported in Table 1.
    [051] The Composition of Inventive Example 3 is an ethylene-hexene copolymer that was prepared via gas phase polymerization process in a simple reactor in the presence of a hafnium-based catalytic system, as described above. The properties of the ethylene-hexene copolymer composition of Composition of Inventive Example 3 are reported in Table 1. Compositions of Comparative Example 1-4
    [052] The Compositions of Comparative Example 1-2 are ethylene-octene copolymers that were prepared via a solution polymerization process in a series-connected dual reactor configuration. The properties of the ethylene-octene copolymer compositions of the Compositions of Comparative Example 1-2 are reported in Table 2.
    [053] The Composition of Comparative Example 3 is an ethylene-octene copolymer that was prepared via a solution polymerization process in a series-connected dual reactor configuration. The properties of the ethylene-octene copolymer composition of the Composition of Comparative Example 3 are reported in Table 2.
    [054] The Composition of Comparative Example 4 is ethylene-octene copolymer that was prepared via solution polymerization process in a simple reactor configuration. The properties of the ethylene-octene copolymer composition of Comparative Example Composition 4 are reported in Table 2. Fabrics of the Invention 1-5 and Comparative Fabrics 1-4
    [055] The Compositions of Inventive Example 1-5 and Compositions of Inventive Example 1-3, as described above, were spun on a Reicofil 4 bicomponent continuous spinning pilot line using 2 extruders while the fibers were drawn to a nominal denier of approximately 2 dpf fiber using a cabin pressure system that started with an initial cabin air pressure of 2700 Pa, and then gradually increased to a maximum cabin pressure, while maintaining stable fiber spinning, that is, 3700 or more, as illustrated by Representative Example Inventive Compositions 2, 4, and 5 to form Inventive Continuous Spinning Nonwovens 1-5 (Inventive Fabrics 1-5) and Comparative Continuous Spinning Nonwovens 1-3 (Comparative Fabrics 1-3). Productivity was kept at a constant level at 0.51 ghm (grams per hole per minute). The die had a hole density of 6,827 holes/meter with each hole having a diameter of 0.6 mm and l/d ratio of 4. Extruder temperatures were set at 220°C and die temperatures at 225°C , with a polymer melting temperature of approximately 230°C. All samples were produced at 20 GSM at a linear fabric production line speed (grams per m2) of 175 meters/min. The mat bonding took place between an embossed (embossed) roll and a smooth roll with a nip pressure of 50N/min, while maintaining the oil temperature of the flat roll 2°C below the temperature of the oil of the embossed roll.
    [056] Fabrics of the Invention 1-5 and Comparative Fabrics 1-3 were tested for their properties and these properties are reported in Table 3 and 4, respectively. Inventive Example Compositions 1A-5A
    [057] Compositions of Inventive Example 1A-2A and 4-5 are ethylene-octene copolymers prepared via solution polymerization process in a dual reactor configuration connected in series in the presence of a catalytic system comprising a metal complex of an aryloxyether polyvalent, as described above. The properties of the ethylene-octene copolymer compositions of Inventive Example Compositions 1A-2A and 4A-5A are reported in Table 1A.
    [058] The Composition of Inventive Example 3A is an ethylene-hexene copolymer that was prepared via gas phase polymerization process in a simple reactor in the presence of a hafnium-based catalytic system, as described above. The properties of the ethylene-hexene copolymer composition of Composition of Inventive Example 3A are reported in Table 1A. Inventive Example Compositions 6A-7A
    [059] Inventive Example Compositions 6A-7A are ethylene-octene copolymers that were prepared via solution polymerization process in a dual reactor configuration connected in series in the presence of a catalytic system comprising a metal complex of a polyvalent aryloxyether, as described above. The properties of ethylene-octene copolymer compositions of Compositions of Inventive Example 6A-7A are reported in Table 1A1. Comparative Example Compositions 1A-2A
    [060] Composition of Inventive Example 1A is ethylene-octene copolymer that was prepared via solution polymerization process in a series-connected dual reactor configuration. The properties of the ethylene-octene copolymer composition of Comparative Example Composition 1A are reported in Table 2A.
    [061] Comparative Example Composition 2A is ethylene-octene copolymer that was prepared via solution polymerization process in a simple reactor configuration. The ethylene-octene copolymer composition properties of Comparative Example Composition 2A are reported in Table 2A. One-component Continuous Filaments of the Invention (IMCF) 1A-7A and Comparative One-Component Continuous Filaments (CMCF) 1A-2A
    [062] The inventive compositions 1A-7A and comparative compositions 1A-2A were formed into Inventive One-Component Continuous Filaments 1A-7A and Comparative One-Component Continuous Filaments 1A-2A, respectively, according to the process described below. The fibers are spun on a Hills Bicomponent Continuous Fiber Spinning Line at a throughput rate of 0.50 ghm. A Hills Bicomponent die is used operating at a 50/50 core/sheath ratio with the same material fed to each extruder, thus forming monocomponent fibers. The matrix configuration consists of 144 holes, with a hole diameter of 0.6 mm and a L/D of 4/1. The cooling air temperature and flow rate are set at 15°C and 30% maximum, respectively. The extruder profiles are adjusted to obtain a melt temperature of 235-238°C. The fiber bundle is wrapped around the godets at least 4 times, with no stretching between the 2 godets, and then evacuated to a vacuum to eliminate any winder-related variability. The Inventive One-Component Continuous Filaments 1A-7A and the Comparative One-Component Continuous Filaments 1A-2A were tested for properties, and the results are shown in Table 3A. Test Methods Test methods include the following: Density
    [063] Samples that are measured for density are prepared in accordance with ASTM D-1928. Measurements are performed within one hour of sample compression using ASTM D-792, Method B. Melt Index
    [064] The melt index, or I2, is measured in accordance with ASTM-D 1238, Condition 190°C/2.16 kg, and is reported in grams eluted over 10 minutes. I10 is measured in accordance with ASTM-D 1238, Condition 190°C/10kg, and is reported in grams eluted over 10 minutes. Gel Permeation Chromatography (GPC)
    [065] The GPC system consists of a Waters (Milford, MA) 150°C high temperature chromatograph (other suitable high temperature GPC instruments include Polymer Laboratories (Shropshire, UK) Model 210 and Model 220) equipped with an on-board differential refractometer (RI). Additional detectors may include a Polymer ChAR IR4 infrared detector (Valencia, Spain), Precision Detectors (Amherst, MA) Model 2040 2-Angle Laser Light Scattering Detector (Amherst, MA), and a Viscotek 150R 4-capillary solution viscometer ( Houston, TX). A GPC system with the last two independent detectors and at least one of the first detectors is sometimes referred to as "3D-GPC", while the term "GPC" alone generally refers to conventional GPC. Depending on the sample, the 15 degree angle or the 90 degree angle of the light scattering detector is used for calculation purposes. Data collection is conducted using Viscotek TriSEC software, Version 3, and a 4-channel Viscotek DM400 Data Manager. The system is also equipped with an online solvent degassing device from Polymer Laboratories (shropshire, UK). Appropriate high temperature GPC columns can be used, such as the four Shodex HT803 columns of 13 microns and 30 cm in length or the four columns from Polymer Labs 30 cm in length, with 20 micron mixed pore size loading (MixA LS , Polymer Labs). The sample carousel compartment at 140°C and the column compartment is operated at 150°C. Samples are prepared at a concentration of 0.1 gram of polymer in 50 milliliters of solvent. The chromatographic solvent and sample preparation solvent contain 200 ppm butylated hydroxytoluene (BHT). The two solvents are sparged with nitrogen. Polyethylene samples are gently shaken at 160°C for four hours. The injection volume is 200 microliters. The flow rate across the entire GPC is adjusted to 1 ml/minute.
    [066] The GPC column set is calibrated before running the Examples, running twenty-one polystyrene standards with narrow molecular weight distribution. The molecular weight (MW) of the standards ranges from 580 to 8,400,000 grams per mole, and the standards are contained in six "cocktail" blends. Each master blend has at least a dozen separations between individual molecular weights. Standard blends are purchased from Polymer Laboratories (Shropshire, UK). Polystyrene standards are prepared at 0.025g in 50ml solvent for molecular weights equal to or greater than 1,000,000 grams per mol and 0.05g in 50ml solvent for molecular weights less than 1,000,000 grams per mol. Polystyrene standards were dissolved at 80oC with gentle agitation for 30 minutes. Narrow standard blends are run first and in descending order of the highest molecular weight component to minimize degradation. Polystyrene standard peak molecular weights are converted to Mw of polyethylene using the Mark-Houwink K equation and values (sometimes referred to as α) mentioned later for polystyrene and polyethylene. See the Examples section for a demonstration of this procedure.
    [067] With 3D-GPC, the weight average molecular weight ("Mw,Abs") and intrinsic viscosity are also independently obtained from suitable narrow polyethylene standards, using the same conditions mentioned above. These linear polyethylene narrow standards can be obtained from Polymer Laboratories (Shropshire, UK; Part Nos. PL2650-0101 and PL2650-0102).
    [068] The systematic method for determining multidetector offsets is conducted in a manner consistent with that published by Balke, Mourey et al. (Mourey and Balke, Chromatography Polym., chapter 12 (1992)) (Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym., chapter 13 (1992)), optimizing the triple detector log results (Mw and intrinsic viscosity) ) of Dow 1683 wide distribution polystyrene (American Polymer Standards Corp.; Mentor, OH) or its equivalent against the narrow standard column calibration results of the Narrow Polystyrene Standards Calibration Curve. Molecular weight data, relating to the determination of detector volume displacement, are obtained in a manner consistent with that published by Zimm (Zimm, BH, J.Chem.Phys., 16, 1099 (1948)) and Kratochvil (Kratochvil) , P., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NY (1987)). The total injected concentration used in determining the molecular weight is obtained from the mass detector area and mass detector constant derived from an appropriate linear homopolymer polyethylene, or one of the polyethylene standards. The calculated molecular weights are obtained using a light scattering constant derived from one or more polyethylene standards mentioned and a refractive index concentration coefficient, dn/dc, of 0.104. Generally, the mass detector response and light scattering constant should be determined from a linear standard with a molecular weight greater than about 50,000 daltons. Calibration of the viscometer can be performed using the methods described by the manufacturer or, alternatively, using published values of linear standards such as Standard Reference Materials (SRM) 1475a, 1482a, 1483 or 1484a. Chromatographic concentrations are considered low enough to eliminate the effects of the second virial coefficient (effects of concentration on molecular weight). Crystallization Elution Fractionation Method (CEF)
    [069] Comonomer distribution analysis is conducted with Crystallization Elution Fractionation (CEF) (PolymerChar in Spain) (B Monrabal et al., Macromol. Symp. 257, 71-79 (2007)). Ortho-dichlorobenzene (ODCB) with 600ppm of antioxidant butylated hydroxytoluene (BHT) is used as a solvent. Sample preparation is performed with an automatic sampler at 160oC for 2 hours under shaking at 4mg/ml (unless otherwise specified). The injection volume is 300μl. The temperature profile of CEF is crystallization at 3oC/min from 110oC to 30oC, thermal equilibrium at 30oC for 5 minutes, elution at 3oC/min from 30oC to 140oC. The flow rate during crystallization is 0.052 ml/min. The flow rate during elution is 0.50 ml/min. Data is collected on the basis of one data point/second.
    [070] The CEF column is loaded by The Dow Chemical Company with 125 μm+/-6% glass beads (MO-SCI Specialty Products) with 1/8" stainless steel tubing. The glass beads are acid washed by the MO-SCI Specialty by request from The Dow Chemical Company Column volume is 2.0 ml Column temperature calibration is conducted using a 1475a linear polyethylene mixture as per NIST Standard Reference Material (1.0mg /ml) and Eicosan (2mg/ml) in ODCB. The temperature is calibrated by adjusting the heating elution rate so that the 1475a NIST linear polyethylene has a peak temperature of 101.0oC and Eicosan a peak temperature of 30 ,0oC CEF column resolution is calculated with a mixture of linear polyethylene 1475a NIST (1.0mg/ml) and hexacontane (Fluka, purum, > 97.0%, 1mg/ml) A line separation is obtained. of hexacontane and 1475a NIST polyethylene base. The area of hexacontane (from 35.0 to 67.0oC) relative to the area of 1475a NIST of 67.0 at 110.0oC it is 50 to 50, and the amount of soluble fraction below 35.0oC is <1.8% by weight. CEF column resolution is defined in the following equation: Resolution= Temp. peak of NIST 1475a-Temp. of hexacontane
    where column resolution is 6.0. Comonomer Distribution Constant Method (DSC)
    [071] The comonomer distribution constant (CDC) is calculated from the comonomer distribution profile through CEF. CDC is defined as the Comonomer Distribution Index divided by the Comonomer Distribution Format Factor, multiplying by 100, as shown in the following equation:

    [072] Comonomer distribution index means the total weight fraction of polymer chains with the comonomer content ranging from 0.5 of the median comonomer content (Cmedian) and 1.5 of Cmedian from 35.0 to 119.0° Ç. Comonomer Distribution Shape Factor is defined as a ratio of half the width of the comonomer distribution profile divided by the standard deviation of the peak temperature comonomer distribution profile (Tp).
    [073] CDC is calculated from the comonomer distribution profile through CEF, and CDC is defined as the Comonomer Distribution Index divided by the Comonomer Distribution Format Factor, multiplying by 100 as shown in the following Equation:
    where comonomer distribution index means the total weight fraction of polymer chains with the comonomer content ranging from 0.5 of the median comonomer content (Cmedian ) and 1.5 of Cmedian from 35.0 to 119.0 C, where the Comonomer Distribution Shape Factor is defined as the ratio of half the width of the comonomer distribution profile divided by the standard deviation of the peak temperature comonomer distribution profile (Tp).
    [074] The CDC is calculated according to the following steps: (A) obtain a fraction by weight at each temperature (T) (wT(T)) from 35.0oC to 119.0oC with a gradual temperature increase of 0.200 °C of CEF according to the following Equation:
    (B) calculate the median temperature (Tmedian) in the cumulative weight fraction of 0.500 according to the following Equation:
    (C) calculate the corresponding median comonomer content in mol % (Cmedian) at the median temperature (Tmedian) using the comonomer content calibration curve according to the following Equation:
    (D) construct a comonomer content calibration curve using a series of reference materials with known amount of comonomer content, ie, eleven reference materials with narrow comonomer distribution (monomodal comonomer distribution in CEF of 35.0 at 119.0oC) with weight average Mw from 35,000 to 115,000 (measured via conventional GPC) at a comonomer content ranging from 0.0 mol% to 7.0 mole % are analyzed with CEF under the same experimental conditions specified in the experimental sections of CEF; (E) calculate the comonomer content calibration using a peak temperature (Tp) of each reference material and its comonomer content. Calibration is calculated for each reference material as shown in the following equation:
    where R2 is the correlation constant; (F) Calculate the Comonomer Distribution Index from the total weight fraction with a comonomer content ranging from 0.5*Cmedian to 1.5*Cmedian, and if Tmedian is greater than 98.0 C, the Index of Comonomer Distribution is set to 0.95; (G) Obtain the maximum peak height of the CEF comonomer distribution profile by searching each data point for the highest peak from 35.0oC to 119.0oC (if the two peaks are identical then the highest temperature peak will be selected low); half-width is defined as the temperature difference between the front temperature and the rear temperature at half the height of the maximum peak, the front temperature at the half of the maximum peak is fetched forward from 35.0oC, while the temperature after half the maximum peak is fetched backward from 119.0oC in the case of a well-defined bimodal distribution, in which the difference in peak temperatures is equal to or greater than 1.1 times the sum of half the width of each peak, the half-width of the ethylene-based polymer composition of the invention is calculated as the arithmetic mean of the half-width of each peak; and (H) calculate the temperature standard deviation (Stdev) according to the following Equation:
    Zero Shear Viscosity Measurement Method via Fluency Test
    [075] The zero shear viscosities are obtained through creep tests, conducted in a controlled tension rheometer AR-G2 (TA Instruments; New Castle, Del) using parallel plates of 25mm in diameter at 190oC. The rheometer oven is set at the test temperature for at least 30 minutes before zeroing the accessories. At the test temperature, the compression molded sample disc is inserted between the plates and allowed to reach equilibrium for 5 minutes. The top plate is then lowered to 50μm above the desired test space (1.5mm). Any superfluous material is trimmed and the top plate lowered into the desired space. Measurements are performed under nitrogen purge at a flow rate of 5L/min. The default fluency period is set to 2 hours.
    [076] A low constant shear stress of 20 Pa is applied to all samples to ensure that the steady state shear rate is low enough to be in the Newtonian region. The resulting steady-state shear rates are on the order of 10-3s-1 for the samples in this study. Steady state is determined by taking linear regression for all data in the last 10% time window of the log(J(t)) vs. graph. log(t), where J(t) is the creep curve and t is the creep time. If the linear regression curve is greater than 0.97, the steady state is considered reached and the fluency test stopped. In all cases in this study, the curve meets the criterion within 2 hours. The steady-state shear rate is determined from the linear regression curve of all data points in the last 10% time window of the ε vs. graph. t, where ε is the deformation. Zero shear viscosity is determined from the ratio of applied stress to steady state shear rate.
    [077] To determine if the sample degrades during the creep test, a small amplitude oscillatory shear test is conducted before and after the creep test on the same specimen from 0.1 to 100 rad/s. The complex viscosity values of the two tests are compared. If the difference in viscosity values at 0.1 rad/s is greater than 5%, the sample is considered to have degraded during the creep test, and the result is discarded. Zero Shear Viscosity Ratio (ZSVR)
    [078] The zero shear viscosity ratio (ZSVR) is defined as the ratio of the zero shear viscosity (ZSV) of the branched polyethylene material to the ZSV of the linear polyethylene material at the equivalent weight average molecular weight (Mw-gpc) as shown in the following Equation:

    [079] The ZSV value is obtained from the creep test at 190°C via the method described above. The Mw-gpc value is determined using the conventional GPC method. The correlation between linear polyethylene ZSV and its Mw-gpc was established based on a series of linear polyethylene reference materials. A description of the ZW-Mw relationship can be found in the ANTEC procedure: Karjala, Teresa P.; Sammler, Robert L.; Mangnus, Marc A.; Hazlitt, Lonnie G.; Johnson, Mark S.; Hagen, Charles M., Jr.; Huang, Joe W.L.; Reichek, Kenneth N. Detection of Low Levels of Long Chain Branching in Polyolefins. Annual Technical Conference - Society of Plastic Engineers (2008), 66th 887-891. 1H NMR Method
    [080] 3.26g of concentrated solution is added to 0.133g of polyolefin sample in 10mm NMR tube. The concentrated solution is a mixture of tetrachloroethane-d2 (TCE) and perchlorethylene (50:50, w:w) with 0.001M Cr3+. The solution in the tube is purged with N2 for 5 minutes to reduce the amount of oxygen. The capped sample tube is left at room temperature overnight to swell the polymer sample. The sample is dissolved at 110°C with stirring. The samples are free from additives that may contribute to unsaturation, such as glidants such as erucamide.
    [081] The 1H NMR is conducted with a 10mm cryoprobe at 120°C on the Bruker AVANCE 400 MHz spectrometer.
    [082] Two experiments are performed to obtain unsaturation: the double pre-saturation control experiments.
    [083] For the control experiment, the data is processed with the exponential window function with LB=1 Hz, and the baseline corrected from 7 to -2 ppm. The TCE residual 1H signal is set to 100, the Itotal integral from -0.5 to 3ppm is used as the total polymer signal in the control experiment. The number of CH2 group in the polymer is calculated as follows: NCH2 = Itotal/2
    [084] For the double presaturation experiment, the data is processed with the exponential window function with LB=1 Hz, the baseline corrected from 6.6 to 4.5 ppm. The residual 1H signal of TCE is set to 100, the corresponding integrals for unsaturation (Ivinylidene, Isubstituted, Ivinyl and Ivinylidene) have been integrated based on the region shown in the graph below.

    [085] Unsaturation unit numbers for vinylene, trisubstituted, vinyl and vinylidene are calculated:
    [086] Ntrisubstituted=Itrisubstituted Nvinyl=Ivinyl/2 The unit of unsaturation/1,000,000 carbons is calculated as follows: Nvinylene/1,000,000C=(Nvinylene/NCH2)*1,000,000 Ntrisubstituted /1,000,000C = (Nt risubstituted / NCH2)*1,000,000 Nvinyl/1,000,000C = (Nvinyl/NCH2)*1,000,000 Nvinylidene/1,000,000C = (Nvinylidene/NCH2)&1,000,000
    [087] The requirement for NMR analysis of unsaturation includes: quantitation level of 0.47 ± 0.02/1,000,000 carbons for Vd2 with 200 scans (data acquisition in less than 1 hour including time to run the experiment control) with 3.9% by weight of the sample (for Vd2 structure, see Macromolecules, vol.38, 6988, 2005), 10mm high temperature cryoprobe. The quantization level is defined as the signal-to-noise ratio of 10.
    [088] The chemical shift reference is set at 6.0 ppm for the 1H residual proton signal of TCT-d2. Control is conducted with pulse ZG, TD 32768, NS4, DS 12, SWH 10,000 Hz, AQ 1.64s, D1 14s. The dual presaturation experiment is conducted with a modified pulse sequence, 01P 1.354 ppm, O2P, 0.960 ppm, PL9 57 db, PL21 70 db, TD 32768, NS 200, DS 4, SWH 10,000 Hz, AQ 1.64s , D1 1s, D13 13s. Modified pulse sequences for unsaturation with Bruker AVANCE 400 MHz spectrometer are shown below.
    Maximum Cab Air Pressure
    [089] In-cab air pressure for continuous spinning was used to attenuate the fibers to the maximum level. The maximum level was selected as the highest cabin air pressure that the fiber curtain could withstand with good spinning stability. Stability was described as the highest air pressure in the cabin in which repeated fiber breakages did not occur, as per visual inspection. Increasing cabin pressure beyond the maximum cabin air pressure would result in repeated fiber breaks. Fiber samples were collected under the conditions of nominal 2 denier, standard cabin air pressure of 2700 Pa, as well as maximum sustainable cabin air pressure or 3700, whichever was less. Connection Window
    [090] The bonding window is determined by the range of surface temperatures or heated oil temperatures of the calender roll and the smooth roll that can be used in the bonding process in preparing a continuous spinning non-woven fabric to achieve balance physical properties (such as tensile strength, abrasion resistance and elongation) of the fabric. Peak bond temperature is determined as the calender roll oil temperature at which the highest MD Peak Tensile Strength is obtained for a continuous spin fabric. Handle-O-Meter
    [091] The Handle-O-Meter is a commercially available device from the Thwing-Albert Company. The Handle-O-Meter measures “feel”, taking into account the combined effects of stiffness or curvature and the surface friction of ply materials such as non-woven fabrics, films/films and laminates. Conditions for evaluation: A 6" x 6" monolayer sample is evaluated using a 100 gm beam assembly and a 5 mm slot width. The fabric is pushed into the slot through the beam and the “touch” is the resistance the fabric exerts on the beam as it pushes it into the slot. Lower touch values indicate softer, more drapeable fabrics. Traction test
    [092] The following procedures are used to generate the tensile test data for nonwovens of the present invention. The basis weight can be determined by measuring the weight of a known area of fabric. For example, basis weight in g/m2 can be determined in accordance with ASTM D 3776. a) Standard Conditioning ERT 60.2-99; b) ERT 130.2 Nonwovens Sampling; c) ERT 20.2-89 and ISO test methods (a) ISO 554 - 76 (E) b) ISO 186:1985.
    [093] The peak tensile strength and elongation at break of non-woven materials are determined using the following procedures. The test method describes two procedures Option A-IST 110.4-02 and Option B - ERT 20.2-89 for conducting tensile tests of non-woven material. These procedures use two types of specimens which are Option A-25 mm (1.0”) Strip Tension and Option B Strip Tension - 50 mm (2.0”). Option B was used in samples in this report. A specimen is attached to a tensile testing machine with a distance between grip jaws of 200 mm, with a force applied to stretch the specimen at a rate of 100 mm/min until it breaks.
    [094] The values of breaking strength and elongation of the specimen are obtained from a computer interface.
    [095] Peak tensile strength is the maximum or peak force applied to a material before failure. Fragile materials often break at full strength. Flexible materials generally face maximum force before breaking. A highly accurate electronic test instrument is used to measure the elongation at break and peak tensile strength of materials while tensile forces are applied to the material. The force exerted on the specimen is read directly on the test machine or graphs obtained during the procedure. For each sample, at least 5 specimens were tested and averaged and used for the peak tensile strength observed for the sample.
    [096] Elongation at break is deformation in the load direction caused by a tensile force. Elongation is expressed as a ratio of the length of the stretched material as a percentage to the length of the unstretched material. Elongation at break is determined at the point where the stretched material breaks. Apparent elongation is determined by the increase in length from the beginning of the force-extension curve to a point corresponding to the breaking force, or other applied force. Apparent elongation is calculated as the percent increase in length based on useful length (Lo)
    Fiber Tensile Test
    [097] Two denier fibers produced to the Hills Fiber Spinning specifications above are tested in accordance with ASTM D 2256. The 144 filaments of the Hills Continuous Filament Fiber Spinning line are tested as a single bundle using MTS Sintech 5/G. Grips/jaws for conventional fibers are used. The grips are set to an initial 8” length. Clamp speed is set at 16”/minute. Five replicas are operated and the peak load recorded as the maximum fiber tensile strength. Elongation at break is recorded as the maximum elongation. Abrasion Resistance
    [098] Abrasion resistance is determined as follows. A non-woven fabric or laminate is rubbed using a Friction Tester to determine the level of lint (“fuzz”). A lower lint level is desirable, meaning the fabric has greater resistance to abrasion. A 11.0 cm x 4.0 cm piece of non-woven fabric is rubbed with sandpaper in accordance with ISO POR 01 106 (Aluminum Oxide Fabric Sandpaper 320 granulation affixed in 2 pound weight, and rubbed for 20 cycles to a rate of 42 cycles per minute) for loose fibers to accumulate on the fabric. Loose fibers were collected with adhesive tape and measured gravimetrically. The lint level is then determined as the total loose fiber weight in grams divided by the tissue sample surface area (44.0 cm2). Abrasion resistance can be optimized for some compositions by exceeding the peak bonding temperature to lightly bond the material. Stretch Capacity
    [099] The ramp-to-break (“Ramp-to-Break”) method is employed to determine the maximum line speed for drawing fibers in a Hills Continuous Filament Spinning line, obtained by increasing the speed of retraction of the filament bundle, thus mechanically stretching the fibers. This is carried out in the ramping method to the point where at least one fiber break occurs. The highest speed at which a material can be operated for at least 30 seconds without fiber breakage is the maximum draw speed or ramp-to-break speed. Ramping Procedure
    [100] The material is ramped from a sufficiently low line speed, eg 1500 mpm or less if necessary. The material is operated at this line speed for 30 seconds and observed for any fiber breaks. If no breaks occur, then the godet speed is ramped at a rate of 500 mom for 30 seconds. The material is operated for 30 seconds at each intermediate point while checking for breakage. This is carried out until a break occurs. The speed at which the break occurs is recorded. The process is repeated a minimum of three times and the average recorded as the maximum draw speed via the ramp-to-break methodology.
    [101] The present invention may be embodied in other forms without departing from its spirit and essential attributes and, consequently, reference is made to the appended claims, rather than the above report, as an indication of the scope of the invention. Table 1





    权利要求:
    Claims (4)
    [0001]
    1. Continuously spinning non-woven cloth comprising one-component fibers prepared with an ethylene-based polymer composition, the non-woven cloth containing the composition characterized in that it comprises: - less than or equal to 100 percent by weight the ethylene-derived units; and - less than 30 percent by weight of units derived from one or more α-olefin comonomers; said ethylene-based polymer composition is defined as having a Comonomer Distribution Constant in the range of more than 100 to 400, a vinyl unsaturation of less than 0.1 vinyl per thousand carbon atoms, present in the main chain of the composition of ethylene-based polymer; a zero shear viscosity ratio (ZSVR) in the range of 1 to less than 2; a density in the range of 0.930 to 0.970 g/cm3, a melt index (I2) in the range of 15 to 30g/10 minutes, a molecular weight distribution (Mw/Mn) in the range of 2 to 3.5, and a molecular weight distribution (Mz/Mn) in the range of less than 2.
    [0002]
    2. Cloth, according to claim 1, characterized in that said monocomponent fiber supports a cabin pressure in the range of at least 3000 Pa.
    [0003]
    3. Cloth according to claim 1, characterized in that it has a peak tensile strength in the machine direction of at least 15 N/5 cm, said non-woven fabric being a 20 GSM fabric prepared to a maximum cabin pressure of at least 3000 Pa.
    [0004]
    4. Continuous spinning non-woven fabric laminated structure, as defined in claim 1, characterized by having the configuration SX, or SXX, or SXXX or SXXXX or SXXXXX, where S is continuous spinning and X can be a film, coating or other non-woven material in any combination.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112014008019B1|2021-08-03|CONTINUOUS SPINNING NON-WOVEN CLOTH AND CONTINUOUS SPINNING NON-WOVEN CLOTH LAMINATE STRUCTURE
    CA2554103C|2010-09-21|Fibers and nonwovens comprising polypropylene blends and mixtures
    US7927698B2|2011-04-19|Fibers and nonwovens comprising polyethylene blends and mixtures
    US8013093B2|2011-09-06|Articles comprising propylene-based elastomers
    BR112012016568B1|2021-01-26|bicomponent fiber composed of a polyethylene-based resin and a high melting point, non-woven resin, textile product, filter media products and battery separator products
    JP2013522491A|2013-06-13|Composite fiber
    US9382411B2|2016-07-05|Propylene polymers
    BR112019019236A2|2020-04-14|polymers for use in fibers and non-woven fabrics, articles thereof and composites thereof
    US20220002924A1|2022-01-06|A non-woven fabric having ethylene/alpha-olefin polymer fibers
    WO2018212211A1|2018-11-22|Crimped fibers and nonwoven cloth
    JP2016516911A|2016-06-09|Fiber containing polyethylene blend
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    同族专利:
    公开号 | 公开日
    MX2014004165A|2014-07-28|
    BR112014008019A2|2017-04-11|
    BR112014008021A2|2017-04-11|
    CN103975099A|2014-08-06|
    KR101960559B1|2019-03-20|
    MX348261B|2017-06-05|
    JP6336908B2|2018-06-06|
    EP2751313A1|2014-07-09|
    EP2751313B1|2018-01-10|
    CN103975099B|2016-03-09|
    JP2014531528A|2014-11-27|
    KR20140072071A|2014-06-12|
    US10391739B2|2019-08-27|
    JP6129190B2|2017-05-17|
    WO2013052636A1|2013-04-11|
    CN103958751B|2016-05-04|
    MX350943B|2017-09-26|
    EP2751315B1|2016-12-07|
    JP2014532125A|2014-12-04|
    WO2013052638A1|2013-04-11|
    KR101963791B1|2019-07-31|
    CN103958751A|2014-07-30|
    BR112014008021B1|2021-04-27|
    US10131114B2|2018-11-20|
    KR20140072070A|2014-06-12|
    MX2014004164A|2014-07-28|
    EP2751315A1|2014-07-09|
    US20140248816A1|2014-09-04|
    US20140248811A1|2014-09-04|
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-08-06| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-02-02| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|
    2021-05-25| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-08-03| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 04/10/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201161543425P| true| 2011-10-05|2011-10-05|
    US61/543,425|2011-10-05|
    PCT/US2012/058708|WO2013052636A1|2011-10-05|2012-10-04|Spunbond nonwoven fabrics|
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