Patent Grant
12006593
The field of this invention is a method of making curly fibers and non-wovens having such fibers, the method including stretching.
Polyethylene based fibers are used in consumer products, especially non-woven fabrics. Such fibers are desirable due its drape-ability and smoothness. Non-woven fabrics have numerous applications, such as filters, disposable materials in medical applications, and diaperstock. To reduce weight of the final product crimping or curling of the fiber has been proposed.
There remains a desire to form fibers having enhanced curliness (also known as crimp) and to be able to do so efficiently.
The inventors have discovered that curliness or crimp is enhanced by choosing specific materials for use in multi-component fibers and also by stretching those fibers. Thus disclosed herein is a process comprising forming fibers each having at least a first region and a second region wherein the first region comprises an ethylene/alpha olefin interpolymer composition characterized by a density in the range of 0.930 to 0.965 g/cm3, a melt index (I2) in the range of from 10 to 60 g/10 minutes, wherein the 12 is measured according to ASTM D1238, 190C, 2.16 kg, a molecular weight distribution, expressed as the ratio of the weight average molecular weight to number average molecular weight (Mw(GPC)/Mn(GPC)) as determined by GPC in the range of from 1.5 to 2.6, a tan delta at 1 radian/second of at least 45, a low temperature peak and a high temperature peak on an elution profile via improved comonomer composition distribution (ICCD) procedure, and a full width at half maximum of the high temperature peak is less than 6.0° C. and stretching the fibers to an elongation of at least 20% thereby increasing curl of the fiber. The process can further include forming a non-woven from the fibers and the stretching of the fibers may occur before or after forming of the non-woven.
Disclosed herein is an efficient process for producing a fiber and/or a non-woven from a fiber having a first region and a second region where the regions are characterized by different responses to stretching and relaxing such that after stretching the curl or crimp in the fiber is increased. One of the regions comprises an ethylene/alpha-olefin interpolymer composition that provides surprisingly good curl or crimp when compared to certain other ethylene based resin systems. The stretching may occur before or after formation of the non-woven.
The fibers useful in this process are multi-component fibers in that they have at least a first region and a second region. The fibers can be bicomponent fibers or the fibers may have three or more components (multi-component fibers). The fibers can have a core sheath configuration wherein a cross section of the fiber shows one region, a core, surrounded by another region, a sheath. In multicomponent fibers there can be one or more inner cores, one or more an inner sheaths and an outer sheath. The fibers can have a segmented pie configuration wherein a cross section of the fiber shows one region occupying a portion, for example a quarter, a third, a half of the cross section and a second region occupies the remainder of the cross section. In a multi-component fiber a third or fourth region may occupy a portion of the pie cross section. In a multi-component fiber, a core sheath configuration may be combined with a segmented pie. For example, the core can have two components in a segmented pie structure surrounded by a sheath. In a multi-component system a third component may be contained within a first or second region in an island in sea configuration. For example, a third component may form discrete regions within a first region that forms a core and is surrounded by a sheath. Each region of the fiber has a centroid and the fiber itself has a centroid. As used herein centroid means the arithmetic mean of all the points of the region of a cross-section of the fiber or a specific region of the fiber. For a concentric core sheath, the core and sheath have the same centroid. The first and second region can have the same centroid. The centroid of the first and the second regions can be the same as the centroid for the overall fiber. Alternatively, the first and second regions can have different centroids. This configuration is be referred to as eccentric. At least one of the regions can have a centroid that can be different from the centroid of the fiber.
Each region comprises a different material each having a 2% secant modulus, E, and a yield stress, σy. The 2% secant modulus of each region or the yield strength of each region or both are different from each other. The difference in the yield stress of the materials of the first and second regions divided by the yield stress of the second region can be at least 0.4, or at least 0.45, or at least 0.5, or at least 0.55 or at least 0.6, and can be no more than 1.0. The difference in the 2% secant modulus of the materials of the first and second regions divided by the 2% secant modulus of the second region can be at least 0.4 or at least 0.45, or at least 0.5 or at least 0.55, and can be no more than 1.0. The absolute value of the quotient for the first yield stress divided by the first 2% secant modulus minus the quotient for the second yield stress divided by the second 2% secant modulus, |σy1/E1-σy2/E2|/(σy2/E2), can be at least 0.01, or at least 0.02, or at least 0.05, or at least 0.07, or at least 0.1, and can be no more than 1.0, or no more than 0.8, or no more than 0.7, or no more than 0.5, or no more than 0.4, or no more than 0.3 where E1 is the 2% secant modulus of the first region material, E2 is the 2% secant modulus of the second region material, σy1 is the yield stress of the first region material and σy2 is the yield stress of the second region material. The 2% secant modulus and a yield stress are measured on the injection molded samples according to ASTM D638.
The Ethylene/Alpha-Olefin Interpolymer Composition
By interpolymer is meant that the polymer is a polymer of two, three or more monomers—i.e. a copolymer, terpolymer, etc. In this case the first monomer is ethylene. The second monomer is an alpha olefin. Such alpha olefins have at least 3 carbon atoms, and, for example, may have up to 20, or up to 10 or up to 8 carbons atoms. Exemplary 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. Optional third, fourth, or more monomers may be alpha-olefins. The interpolymer compositions are bimodal and can be conveniently made by combining two ethylene/alpha olefin interpolymers having different molecular weights and/or different densities and/or at least two different peaks in ICCD elution as described in more detail below.
The interpolymers can be random interpolymers. The interpolymer can comprise at least 50 mole percent or at least 60 mole percent or at least 70 mole percent of ethylene based repeat units based on total moles of repeat units in the interpolymer. The interpolymer can comprise no more than 99.9 or no more than 99.5 or no more than 99, or no more than 95, or no more than 90 or no more than 85 mole percent ethylene based repeat units based on total moles of repeat units in the interpolymer. The interpolymer can comprise at least 0.1 or at least 0.5 or at least 1 or at least 5 or at least 10 mole percent of alpha olefin based repeat units based on total moles of repeat units in the interpolymer (i.e. the second and optional third and fourth monomers). The interpolymer can comprise no more than 50 or no more than 30 mole percent of alpha olefin based repeat units based on total moles of repeat units in the interpolymer (i.e. the second and optional third and fourth monomers).
These ethylene/alpha-olefin interpolymer compositions are characterized in certain embodiments by a density of at least 0.930 g/cm3 and no more than 0.965 g/cm3 or no more than 0.960 or no more than 0.955 or no more than 0.950 or no more than 0.945 or no more than 0.940 g/cm3. Density is measured according to ASTM D792. Bicomponent fibers comprising the disclosed ethylene/alpha olefin interpolymer, can show higher curvature. The bimodal polymer compositions can be characterized by a lower density fraction having a density in the range of about 0.900 to about 0.940 g/cm3 and a higher density fraction having a density of at least about 0.950 g/cm3.
These ethylene/alpha-olefin interpolymer compositions can be characterized by a melt index (I2) in the range of from 10 to 60 g/10 minutes, wherein the I2 is measured according to ASTM D1238, 190° C., 2.16 kg. In addition, the ratio of the I10/I2 can be less than 6.9 or 6.8 or 6.7, wherein I10 is measure according to ASTM D1238, 190° C., 10 kg. Lower I10/I2 ratio can indicate lower long chain branching that leads to better spinnability/process ability.
These ethylene/alpha-olefin interpolymer compositions can be characterized by a molecular weight distribution by the method set forth below, expressed as the ratio of the weight average molecular weight to number average molecular weight (Mw(GPC)/Mn(GPC)) in the range of no more than 2.6 or no more than 2.5 and at least 1.5 or at least 1.7 or at least 2.0. Interpolymer compositions having a molecular weight distribution in this range are believed to have better processability (e.g. fiber spinning) than interpolymers having a higher molecular weight distribution. The ethylene/alpha olefin interpolymer can be characterized by a Mw(GPC)/Mn(GPC) greater than (I10/I2)−4.63.
The ethylene/alpha-olefin interpolymer compositions can have a weight average molecular weight from a lower limit of 15,000 g/mol, 20,000 g/mol, or 30,000 g/mol to an upper limit of 100,000 g/mol 120,000 g/mol, or 150,000 g/mol. The Mz(GPC)/Mw(GPC) can be less than 3.0 or less than 2.0 and can be more than 1.0. The bimodal polymer composition can show two different peaks in ICCD elution. The higher temperature fraction can have a peak position molecular weight of no more than 70,000 g/mol, or no more than 50,000 g/mol. The higher temperature fraction can have a peak position molecular weight of at least 15,000 or at least 20,000 g/mol. The lower temperature fraction can have a peak position molecular weight of at least 30000 or at least 40,000 or at least 50,000 g/mol. The lower temperature fraction can have a peak position molecular weight of no more than 250,000 or 200,000 or 150,000 g/mol.
These ethylene/alpha-olefin interpolymer compositions can be characterized by a tan delta (tan δ) at 1 radian/second of at least 45 or at least 50. In addition, these ethylene/alpha-olefin interpolymers can be characterized by a ratio of tan delta at 1 radian/second and 190° C. to tan delta at 100 radians/second and 190° C. of at least 12. These characteristics can be measured by dynamic mechanical spectroscopy (DMS).
These ethylene/alpha-olefin interpolymer compositions can be characterized by at least two distinguishable peaks between 35° C. to 110° C. on the elution profile of improved comonomer composition distribution (ICCD) with a distinct valley (drop of at least 10% compared to the peak height of the smaller peak) between the peaks, wherein the peak positions must be separated by a minimum of 10° C. Each peak is separated by a vertical line at the lowest height point of the adjoining valley.
The peak temperature of the lower temperature peak can be at least 50° C. or at least 60° C. and can be less than 90° C. or less than 75° C. The peak temperature of the higher temperature peak can be at least 90° C. or at least 95° C. and can be less than 110° C. or 105° C. or 100° C. The inventors have found that lower temperature peaks in the range of 50 to 75° C. can be particularly useful in making curly fiber.
The weight fraction of the low temperature peak fraction can be at least 25 or at least 30 and less than 65 or less than 60 or less than 55 weight percent based on total weight of the eluted polymer. The weight fraction of the high temperature peak fraction can be at least 35 or at least 40 or at least 45 and no more than 75 weight percent based on total weight of the eluted polymer.
The full width at half maximum of the high temperature peak can be less than 6.0° C. A narrow peak for the high density fraction denotes a narrower composition distribution without ultra-high or ultra-low molecular weight species that could impede spinning performance or create extractables.
The ethylene/alpha olefin composition can have a composition distribution breadth index (CDBI) of less than 0.5 (i.e. less than 50%), less than 0.3 (30%), less than 0.25 (25%), less than 0.22 (22%) or less than 0.2 (20%).
The ethylene/alpha-olefin interpolymer composition can have a comonomer distribution constant (CDC) of less than 100, preferably 30-80.
The ethylene/alpha-olefin interpolymer compositions can be characterized by molecular weighted comonomer distribution index (MWCDI) of greater than 0.20, or greater than 0.25 or greater than 0.30 or greater than 0.35, or greater than 0.40 or greater than 0.45 or greater than 0.50. MWCDI is a measure of the slope of comonomer incorporation as a function of molecular weight obtained from conventional gel permeation chromatography. If MWCDI is greater than 0.25 (between a molecular weight range of 20,000 and 200,000 g/mol), the resin structure is viewed as having a significant reverse comonomer incorporation with more comonomer on the higher molecular weight side of the distribution.
The ethylene/alpha olefin interpolymer compositions disclosed herein can be characterized by low amounts of long chain branching (LCB). This can be indicated by low zero shear viscosity ratios (ZSVR). Specifically, the ZSVR can be less than 1.35 or no more than 1.30. The ZSVR can be at least 1.10.
The ethylene/alpha olefin interpolymer compositions can be characterized by a vinyl saturation number per 1,000,000 carbon atoms of less than 230, or less than 210, or less than 190, or less than 170, or less than 150 as determined by 1H-NMR.
Any conventional polymerization processes may be employed to produce the ethylene/α-olefin interpolymer composition. Such conventional polymerization processes include, but are not limited to, solution polymerization process, using one or more conventional reactors e.g. loop reactors, isothermal reactors, stirred tank reactors, batch reactors in parallel, series, and/or any combinations thereof. Such conventional polymerization processes also include gas-phase, solution or slurry polymerization or any combination thereof, using any type of reactor or reactor configuration known in the art.
In general, the solution phase polymerization process occurs in one or more well-mixed reactors such as one or more isothermal loop reactors or one or more adiabatic reactors at a temperature in the range of from 115 to 250° C.; for example, from 115 to 200° C., and at pressures in the range of from 300 to 1000 psi; for example, from 400 to 750 psi. In a dual reactor, for example the temperature in the first reactor can be in the range of from 115 to 190° C., or from 115 to 150° C., and the second reactor temperature can be in the range of 150 to 200° C., or 170 to 195° C. In in a single reactor, the temperature in the reactor can be in the range of from 115 to 190° C., or from 115 to 150° C. The residence time in solution phase polymerization process is typically in the range of from 2 to 30 minutes; for example, from 10 to 20 minutes. Ethylene, solvent, hydrogen, one or more catalyst systems, optionally one or more co-catalysts, and optionally one or more comonomers are fed continuously to one or more reactors. Exemplary solvents include, but are not limited to, isoparaffins. For example, such solvents are commercially available under the name ISOPAR E from ExxonMobil Chemical Co., Houston, Texas The resultant mixture of the ethylene/alpha-olefin interpolymer and solvent is then removed from the reactor and the ethylene/alpha-olefin interpolymer is isolated. Solvent is typically recovered via a solvent recovery unit, i.e. heat exchangers and vapor liquid separator drum, and is then recycled back into the polymerization system.
The ethylene/α-olefin interpolymer composition may be produced via solution polymerization in a dual reactor system, for example a dual loop reactor system, wherein ethylene and optionally one or more α-olefins are polymerized in the presence of one or more catalyst systems. Additionally, one or more co-catalysts may be present.
The ethylene/alpha-olefin interpolymers may be produced via solution polymerization in a single reactor system, for example a single loop reactor system, wherein ethylene and optionally one or more α-olefins are polymerized in the presence of one or more catalyst systems. Two different catalysts can be used in a dual reactor system. One or both of the two different catalysts have the formula (I) as shown below. This allows for manufacture of the bimodal interpolymer compositions as described above.
An exemplary catalyst system suitable for producing the first ethylene/a olefin interpolymer can be a catalyst system comprising a procatalyst component comprising a metal-ligand complex of formula (I):
In formula (I), M is a metal chosen from titanium, zirconium, or hafnium, the metal being in a formal oxidation state of +2, +3, or +4; n is 0, 1, or 2; when n is 1, X is a monodentate ligand or a bidentate ligand; when n is 2, each X is a monodentate ligand and is the same or different; the metal-ligand complex is overall charge-neutral; each Z is independently chosen from —O—, —S—, —N(RN)—, or —P(RP)—; L is (C1-C40)hydrocarbylene or (C1-C40)heterohydrocarbylene, wherein independently each RN and RP is (C1-C30)hydrocarbyl or (C1-C30)heterohydrocarbyl, and wherein the (C1-C40)hydrocarbylene has a portion that comprises a 1-carbon atom to 10-carbon atom linker backbone linking the two Z groups in Formula (I) (to which L is bonded) or the (C1-C40)heterohydrocarbylene has a portion that comprises a 1-atom to 10-atom linker backbone linking the two Z groups in Formula (I), wherein each of the 1 to 10 atoms of the 1-atom to 10-atom linker backbone of the (C1-C40)heterohydrocarbylene independently is a carbon atom or heteroatom, wherein each heteroatom independently is O, S, S(O), S(O)2, Si(RC)2, Ge(RC)2, P(RC), or N(RC), wherein independently each RC is (C1-C30)hydrocarbyl or (C1-C30)heterohydrocarbyl; R1 and R8 are independently selected from the group consisting of —H, (C1-C40)hydrocarbyl, (C1-C40)heterohydrocarbyl, —Si(RC)3, —Ge(RC)3, —P(RP)2, —N(RN)2, —ORC, —SRC, —NO2, —CN, —CF3, RCS(O)—, RCS(O)2—, (RC)2C═N—, RCC(O)O—, RCOC(O)—, RCC(O)N(RN)—, (RN)2NC(O)—, halogen, and radicals having formula (II), formula (III), or formula (IV):
In formulas (II), (III), and (IV), each of R31-35, R41-48, or R51-59 is independently chosen from (C1-C40)hydrocarbyl, (C1-C40)heterohydrocarbyl, —Si(RC)3, —Ge(RC)3, —P(RP)2, —N(RN)2, —N═CHRC, —ORC, —SRC, —NO2, —CN, —CF3, RCS(O)3, RCS(O)2—, (RC)2C═N—, RCC(O)O—, RCOC(O)—, RCC(O)N(RN)—, (RN)2NC(O)—, halogen, or —H, provided at least one of R1 or R8 is a radical having formula (II), formula (III), or formula (IV) where RC, RN, and RP are as defined above.
In formula (I), each of R2-4, R5-7, and R9-16 is independently selected from (C1-C40)hydrocarbyl, (C1-C40)heterohydrocarbyl, —Si(RC)3, —Ge(RC)3, —P(RP)2, —N(RN)2, —N═CHRC, —ORC, —SRC, —NO2, —CN, —CF3, RCS(O)—, RCS(O)2—, (RC)2C═N—, RCC(O)O—, RCOC(O)—, RCC(O)N(RN)—, (RC)2NC(O)—, halogen, and —H where RC, RN, and RP are as defined above.
The catalyst system comprising a metal-ligand complex of formula (I) may be rendered catalytically active by any technique known in the art for activating metal-based catalysts of olefin polymerization reactions. For example, the comprising a metal-ligand complex of formula (I) may be rendered catalytically active by contacting the complex to, or combining the complex with, an activating co-catalyst. Activating co-catalysts for use herein include alkyl aluminums; polymeric or oligomeric alumoxanes (also known as aluminoxanes); neutral Lewis acids; and non-polymeric, non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions). Anactivating technique is bulk electrolysis. Combinations of one or more of the foregoing activating co-catalysts and techniques are also contemplated. The term “alkyl aluminum” means a monoalkyl aluminum dihydride or monoalkylaluminum dihalide, a dialkyl aluminum hydride or dialkyl aluminum halide, or a trialkylaluminum. Examples of polymeric or oligomeric alumoxanes include methylalumoxane, triisobutylaluminum-modified methylalumoxane, and isobutylalumoxane.
Lewis acid activators (co-catalysts) include Group 13 metal compounds containing from 1 to 3 (C1-C20) hydrocarbyl substituents as described herein. Examples of Group 13 metal compounds are tri((C1-C20)hydrocarbyl)-substituted-aluminum or tri((C1-C20)hydrocarbyl)-boron compounds; tri(hydrocarbyl)-substituted-aluminum, tri((C1-C20)hydrocarbyl)-boron compounds; tri((C1-C10)alkyl)aluminum, tri((C6-C18)aryl)boron compounds; and halogenated (including perhalogenated) derivatives thereof. Other examples of Group 13 metal compounds are tris(fluoro-substituted phenyl)boranes, tris(pentafluorophenyl)borane. The activating co-catalyst can be a tris((C1-C20)hydrocarbyl borate (e.g. trityl tetrafluoroborate) or a tri((C1-C20)hydrocarbyl)ammonium tetra((C1-C20)hydrocarbyl)borane (e.g. bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borane). As used herein, the term “ammonium” means a nitrogen cation that is a ((C1-C20)hydrocarbyl)4N+a ((C1-C20)hydrocarbyl)3N(H)+, a ((C1-C20)hydrocarbyl)2N(H)2+, (C1-C20)hydrocarbylN(H)3+, or N(H)4+, wherein each (C1-C20)hydrocarbyl, when two or more are present, may be the same or different.
Combinations of neutral Lewis acid activators (co-catalysts) include mixtures comprising a combination of a tri((C1□C4)alkyl)aluminum and a halogenated tri((C6□C18)aryl)boron compound, especially a tris(pentafluorophenyl)boraneor combinations of such neutral Lewis acid mixtures with a polymeric or oligomeric alumoxane, and combinations of a single neutral Lewis acid, especially tris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxane. Ratios of numbers of moles of (metal-ligand complex):(tris(pentafluoro-phenylborane):(alumoxane) [e.g., (Group 4 metal-ligand complex):(tris(pentafluoro-phenylborane):(alumoxane)] are from 1:1:1 to 1:10:30, in other embodiments, from 1:1:1.5 to 1:5:10.
The catalyst system comprising the metal-ligand complex of formula (I) may be activated to form an active catalyst composition by combination with one or more co-catalysts, for example, a cation forming co-catalyst, a strong Lewis acid, or combinations thereof. Suitable activating co-catalysts include polymeric or oligomeric aluminoxanes, especially methyl aluminoxane, as well as inert, compatible, noncoordinating, ion forming compounds. Exemplary suitable co-catalysts include, but are not limited to: modified methyl aluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-) amine, and combinations thereof.
One or more of the foregoing activating co-catalysts can be used in combination with each other. A preferred combination is a mixture of a tri((C1-C4)hydrocarbyl)aluminum, tri((C1-C4)hydrocarbyl)borane, or an ammonium borate with an oligomeric or polymeric alumoxane compound. The ratio of total number of moles of one or more metal-ligand complexes of formula (I) to total number of moles of one or more of the activating co-catalysts can be from 1:10,000 to 100:1. For example, the ratio can be at least 1:5000, or at least 1:1000; and no more than 10:1, or no more than 1:1. When an alumoxane alone is used as the activating co-catalyst, preferably the number of moles of the alumoxane that are employed can be at least 100 times the number of moles of the metal-ligand complex of formula (I). When tris(pentafluorophenyl)borane alone is used as the activating co-catalyst, the number of moles of the tris(pentafluorophenyl)borane that are employed to the total number of moles of one or more metal-ligand complexes of formula (I) can be from 0.5: 1 to 10:1, from 1:1 to 6:1, or from 1:1 to 5:1. The remaining activating co-catalysts are generally employed in approximately mole quantities equal to the total mole quantities of one or more metal-ligand complexes of formula (I).
The Fibers and Non-Woven
At least 75%, or at least 80%, or at least 85%, or at least 90%, or at least 95%, or at least 97%, or at least 98%, or at least 99%, or 100% (all percents being by weight) of the first component of the fiber can be the ethylene/alpha-olefin interpolymer. The remainder of the first component may be additional components such as one or more other polymers and/or one or more additives. Other polymers could be another polyethylene (e.g. polyethylene homopolymer or ethylene/alpha-olefin interpolymer), propylene-based polymer (e.g. polypropylene homopolymer, propylene-ethylene copolymer, or propylene/alpha-olefin interpolymer). The amount of the other polymer may be up to 25%. Potential additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, fillers such as TiO2 or CaCO3, opacifiers, nucleators, processing aids, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, anti-blocks, slip agents, tackifiers, fire retardants, anti-microbial agents, odor reducer agents, anti-fungal agents, and combinations thereof. The ethylene/alpha-olefin interpolymer composition may contain from about 0.01 or from 0.1 or from 1 to about 25 or to about 20 or to about 15 or to about 10 percent by the combined weight of such additives, based on the weight of the ethylene/alpha-olefin interpolymer composition including such additives.
The other region can comprise a different polyolefin or a polyester. For example, the other region may be a polypropylene based polymer, polypropylene, polyethylene terephthalate, or polybutylene terephthalate. The remainder of the second region may be additional components such as one or more other polymers and/or one or more additives. Other polymers could be another polyolefin or another polyester, such as polypropylene, or polyester (e.g. polyethylene terephthalate or polybutylene terephthalate) with or without additives as described above. Potential additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, fillers such as TiO2 or CaCO3, opacifiers, nucleators, processing aids, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, anti-blocks, slip agents, tackifiers, fire retardants, anti-microbial agents, odor reducer agents, anti-fungal agents, and combinations thereof. The ethylene/alpha-olefin interpolymer polymer composition may contain from about 0.01 or from about 0.1 or from about 1 to about 25 or to about 20 or to about 15 or to about 10 percent by the combined weight of such additives, based on the weight of the ethylene/alpha-olefin interpolymer composition including such additives.
The weight ratio of the first component or region to the second component or region can be at least 5/95 or at least 10/90 or at least 20/80 or at least 30/70 or at least 40/60 and can be no more than 95/5 or no more than 90/10 or no more than 80/20 or no more than 70/30 or no more than 60/40.
The fibers as taught herein may be formed by any conventional spinning technique. The fibers as disclosed herein can have one or more of the following characteristics: The fibers may have diameters of at least 5 microns, or at least 10 microns and less than 50 microns, or less than 30 microns. The fibers may have a denier in a denier per filament in the range of less than 50 g/9000 m. All individual values and subranges from less than 50 g/9000 m are included herein and disclosed herein; for example, the denier per filament can be from a lower limit of 0.1, 0.5, 1, 5, 10, 15, 17, 20, 25, 30, 33, 40, or 44 g/9000 m to an upper limit of 0.5, 1, 5, 10, 15, 17, 20, 25, 30, 33, 40, 44, or 50 g/9000 m. For example, the fibers may have a denier per filament in the range of less than 40 g/9000 m; or in the alternative, the fibers may have a denier per filament in the range of less than 30 g/9000 m; or in the alternative, the fibers may have a denier per filament in the range of less than 20 g/9000 m; or in the alternative, the fibers may have a denier per filament in the range of less than 10 g/9000 m; or in the alternative, the fibers may have a denier per filament in the range from 0.5 to 10 g/9000 m.
The bicomponent fibers can be spun through the fine orifices in a metallic plate called spinneret into air or other gas, where it is cooled and solidified forming continuous inventive bi-component fibers. Then the continuous fibers cam be guided into and stretched between a set of rotating rollers or godets having different rotating speeds. The fibers can be stretched between the rollers or godets to at least 20%, or at least 30% or at least 40% or at least 50% or at least 75% elongation. The fibers can be stretched to no more than 800% or no more than 700% or no more than 600% or no more than 500% or no more than 400% or no more than 250% or no more than 200% or no more than 150% or no more than 100% elongation. The stretching can be performed on fibers at ambient temperature.
The fibers can be cut in to short fibers. While stretching may occur after cutting in the alternative, stretching before cutting is efficient. The cut fiber may have lengths of, for example, at least 0.2, or at least 0.5 or at least 1 cm and no more than 16 or 12 or 10 cm. The resulting short fibers can be subsequently fabricated into nonwoven fabrics through carded web process, airlaid process and the bonding process may be but is not limited to thermo-calendering process, adhesive bonding process, hot air bonding process, needle punch process, hydroentangling process, and combinations thereof.
The bicomponent fibers can be spun through the fine orifices in a metallic plate called spinneret into air or other gas, where it is cooled and solidified forming continuous inventive bi-component fibers. The solidified fibers may be drawn off pneumatically through an air stream, and then laid down on a conveyer belt to form a nonwoven fabric web. The nonwoven fabric web can be stretched through MDO (machine direction orientation) process or ring rolling process before or after the bonding process. The bonding process includes but not limited to thermo-calendering process, adhesive bonding process, hot air bonding process, needle punch process, hydroentangling process, and combinations thereof. The nonwoven fabric web can be stretched to at least 20%, or at least 30% or at least 40% or at least 50% or at least 75% elongation. The nonwoven fabric web can be stretched according to certain embodiments to no more than 800% or no more than 700% or no more than 600% or no more than 500% or no more than 400% or no more than 250% or no more than 200% or no more than 150% or no more than 100% elongation. The stretching can be performed on fibers at ambient temperature.
The non-woven as disclosed herein can be made by any known method. Such methods include, but are not limited to, spunbond process, carded web process, airlaid process and bonded according to a process that may be but is not limited to thermo-calendering process, adhesive bonding process, hot air bonding process, needle punch process, hydroentangling process, and combinations thereof. The non-woven disclosed herein may be formed directly from the constituent polymer material(s) by spunbond processing. In spunbond process, the fabrication of non-woven fabric includes the following steps: (a) extruding strands of one or more polymeric compositions from a spinneret; (b) quenching the strands of the one or more polymeric compositions with a flow of air which is generally cooled in order to hasten the solidification of the molten strands of the one or more polymeric compositions; (c) attenuating the filaments by advancing them through the quench zone with a draw tension that can be applied by either pneumatically entraining the filaments in an air stream or by wrapping them around mechanical draw rolls of the type commonly used in the textile fibers industry; (d) collecting the drawn strands into a web on a foraminous surface, e.g. moving screen or porous belt; and (e) bonding the web of loose strands into the non-woven fabric. Bonding can be achieved by a variety of means including, but not limited to, thermo-calendering process, adhesive bonding process, hot air bonding process, needle punch process, hydroentangling process, and combinations thereof.
Staple fibers can be blended, “opened” in a multistep process, dispersed on a conveyor belt, and spread in a uniform web by a wetlaid, airlaid, or carding/crosslapping process. Wetlaid operations typically use about 0.2 to 2 cm long fibers, but sometimes longer if the fiber is stiff or thick. Airlaid processing generally uses about 1 to about 10 cm long fibers. Carding operations typically use 3-4 cm long fibers. Staple nonwovens are bonded either thermally or by using resin. Bonding can be throughout the web by resin saturation or overall thermal bonding or in a distinct pattern via resin printing or thermal spot bonding. Conforming with staple fibers usually refers to a combination with melt blowing, often used in high-end textile insulations.
After forming the non-woven it is stretched in at least one direction. For example, the non-woven can be stretched by ring rolling or using two rollers with differentiated speed. If roller speed for collecting the web is adjusted this can be used to stretch in the machine direction (MD). To stretch in the cross direction, the web can be attached to a roll or mechanism across the web. Stretching preferably occurs at temperatures of at least 5 or at least 10 or at least 15° C. and temperatures no more than 90 or no more than 80 or no more than 60 or no more than 50 or no more than 30° C. The non-woven should be stretched to at least 20% elongation, or at least 30%, or at least 50% or at least 75% but not more than 800%, not more than 700%, not more than 500% or not more than 400% or not more than 300%.
Desirably, in stretching the non-woven at least some portion of the fibers cam be stretched to elongation of to at least 20%, or at least 30% or at least 40% or at least 50% or at least 75% elongation and no more than 700% or no more than 600% or no more than 500% or no more than 400% or no more than 300% or no more than 250% or no more than 200% or no more than 150% or no more than 100% elongation.
According to certain embodiments, the fibers are characterized by a curl of greater than 1 or greater than 1.5 or greater than 2 or greater than 2.5 or greater than 3 mm−1.
The spunbond non-woven fabrics can be formed into multilayer or laminate structures. Such multilayer structures comprise at least 2 or more layers, wherein at least one or more layers are spunbond non-woven as disclosed herein, and one or more other layers are selected from one or more meltblown non-woven layers, one or more wet-laid non-woven layers, one or more air-laid non-woven layers, one or more webs produced by any nonwoven or melt spinning process, one or more film layers. Such as cast film, blown film, one or more coating layers derived from a coating composition via, for example, extrusion coating, spray coating, gravure coating, printing, dipping, kiss rolling, or blade coating. The laminate structures can be joined via any number of bonding methods; thermal bonding, adhesive lamination, hydroentangling, needle punching. Structures can range from S to SX, or SXX, or, SXXX, or SXXXX, or SXXXXX, where S is the non-woven as disclosed herein and X can be a film, coating, or other non-woven material in any combination or one or more of X could also be S. Additional spunbond layers can be made from the ethylene/alpha-olefin interpolymer composition, as described herein, and optionally in combinations with one or more polymers and/or additives.
Testing Methods
Density
Density measurements for the ethylene/alpha-olefin interpolymers were made in accordance with ASTM D792, Method B.
Melt Index (I2) and (I10)
Melt index (I2) values for the ethylene/alpha-olefin interpolymers are measured in accordance with ASTM D1238 at 190° C. at 2.16 kg. Similarly, melt index (I10) values for the ethylene/alpha-olefin interpolymers are measured in accordance with ASTM D1238 at 190° C. at 10 kg. The values are reported in g/10 min, which corresponds to grams eluted per 10 minutes.
Dynamic Mechanical Spectroscopy (DMS)
Samples are compression-molded into 3 mm thick×25 mm diameter circular plaque at 177° C. for five minutes, under 10 MPa pressure. The sample are then taken out of the press and placed on a countertop to cool. Constant temperature, frequency sweep measurements are performed on the compression molded plaques with an ARES strain controlled rheometer (TA Instruments), equipped with 25 mm parallel plates, under a nitrogen purge. For each measurement, the rheometer is thermally equilibrated, for at least 30 minutes, prior to zeroing the gap. The sample disk is placed on the plate, and allowed to melt for five minutes at 190° C. The plates are then closed to 2 mm gap, the sample is trimmed, and then the test is started. The method can have an additional five minute delay built in, to allow for temperature equilibration. The experiments are performed at 190° C., over a frequency range from 0.1 to 100 radian/second, at five points per decade interval. The strain amplitude is constant at 10%. The stress response is analyzed in terms of amplitude and phase, from which the storage modulus (G′), loss modulus (G″), complex modulus (G*), dynamic viscosity (η*), and tan δ (or tan delta) are calculated. Tan delta at 1 radian/second and tan delta at 100 radian/second are obtained.
Improved Comonomer Composition Distribution (ICCD)
The Improved Comonomer Composition Distribution (ICCD) test is performed with Crystallization Elution Fractionation instrumentation (CEF) (PolymerChar, Spain) equipped with IR-5 detector (PolymerChar, Spain) and two-angle light scattering detector Model 2040 (Precision Detectors, currently Agilent Technologies). The ICCD column is packed with gold coated nickel particles (Bright 7GNM8-NiS, Nippon Chemical Industrial Co.) in a 15 cm (length)×¼″ (ID) stainless tubing. The column packing and conditioning are with a slurry method according to the reference (Cong, R.; Parrott, A.; Hollis, C.; Cheatham, M. WO2017040127A1). The final pressure with trichlorobenzene (TCB) slurry packing is 150 bars. The column is installed just before IR-5 detector in the detector oven. Ortho-dichlorobenzene (ODCB, 99% anhydrous grade or technical grade) is used as eluent. Silica gel 40 (particle size 0.2˜0.5 mm, catalogue number 10181-3) is obtained from EMD Chemicals and can be used to dry ODCB solvent The ICCD instrument is equipped with an autosampler with nitrogen (N2) purging capability. ODCB is sparged with dried N2 for one hour before use. Sample preparation is done with autosampler at 4 mg/ml (unless otherwise specified) under shaking at 160° C. for 1 hour. The injection volume is 300 μl. The temperature profile of ICCD is: crystallization at 3° C./min from 105° C. to 30° C., then thermal equilibrium at 30° C. for 2 minutes (including Soluble Fraction Elution Time being set as 2 minutes), followed by heating at 3° C./min from 30° C. to 140° C. The flow rate during elution is 0.50 ml/min. Data are collected at one data point/second. Column temperature calibration can be performed by using a mixture of the reference material linear homopolymer polyethylene (having zero comonomer content, melt index (I2) of 1.0 g/10 min, polydispersity Mw(GPC)/Mn(GPC) approximately 2.6 by conventional gel permeation chromatography, 1.0 mg/ml) and Eicosane (2 mg/ml) in ODCB. ICCD temperature calibration consists of four steps: (1) Calculating the delay volume defined as the temperature offset between the measured peak elution temperature of Eicosane minus 30.00° C.; (2) Subtracting the temperature offset of the elution temperature from the ICCD raw temperature data. It is noted that this temperature offset is a function of experimental conditions, such as elution temperature, elution flow rate, etc.; (3) Creating a linear calibration line transforming the elution temperature across a range of 30.00° C. and 140.00° C. so that the linear homopolymer polyethylene reference has a peak temperature at 101.0° C., and Eicosane has a peak temperature of 30.0° C.; (4) For the soluble fraction measured isothermally at 30° C., the elution temperature below 30.0° C. is extrapolated linearly by using the elution heating rate of 3° C./min according to the reference (Cerk and Cong et al., U.S. Pat. No. 9,688,795).
The comonomer content calibration curve (comonomer content in mole percent versus elution temperature (T)) of ICCD is constructed by using 12 reference materials (a linear ethylene homopolymer and 11 ethylene-octene random copolymers made with single site metallocene catalyst, having a weight average molecular weight ranging from 35,000 to 128,000 g/mol) with known comonomer contents. All of these reference materials are analyzed in the same way as specified previously at 4 mg/mL. The comonomer content in mole percent and its peak temperature on the elution curve follows
Determination of Peaks and Full Width at Half Maximum on the ICCD Elution Profile
A single baseline is subtracted from the IR measurement signal in order to create a relative mass-elution profile plot starting and ending at zero relative mass at its lowest and highest elution temperatures (typically between 35° C. and 119° C.). For convenience, this is presented as a normalized quantity with respect to an overall area equivalent to 1. In the relative mass-elution profile plot from ICCD, a weight fraction (wT(T)) at each temperature (T) can be obtained. The profile (wT(T) vs. T) is from 35.0° C. to 119.0° C. with a temperature step increase of 0.200° C. from the ICCD, and follows
∫35.0119.0wT(T)dT=1 Eq. 2
On the wT(T) vs. T elution profile, a single peak is defined as a curve with one Highest Point in the middle and two Lowest Points on two sides (lower temperature side and higher temperature side). Both heights of the two Lowest Points need to be lower than the height of the Highest Point by at least 10%. If one or both of the Lowest Points have a height less than 10% lower than the height of the Highest Point, i.e. one or both of the Lowest Points have a height greater than 90% of the height of the Highest Point, such a curve is considered a shoulder associated with another peak, but is not a peak itself. Each separate peak is then measured for width in degree C. at 50% of the maximum height of that peak in the wT(T) vs. T elution profile plot. This width is called the full width at half maximum of the peak.
If the ICCD elution profile has multiple peaks, the separation points (Tseparation) between the peaks can be defined as the Lowest Points of the adjacent two peaks. The weight fraction of the nth peak (WTpeak n) can be calculated according to the following equations
WTpeak 1=∫35.0T
WTpeak 2=∫T
. . .
WTpeak n=∫T
where the peak 1, peak 2, . . . , and peak n are the peaks in the order from low temperature to high temperature, and the Tseparation, n is the separation point between the n peak and n+1 peak. Full width at half maximum is defined as the temperature difference between the first intersection of the front temperature and the first intersection of the rear temperature at half of the maximum peak height of that individual peak. The front temperature at the half of the maximum peak is searched forward from 35.0° C., while the rear temperature at the half of the maximum peak is searched backward from 119.0° C.
Comonomer Distribution Constant (CDC)
Comonomer distribution constant (CDC) is calculated from wT(T) vs. T elution profile by ICCD according to the following steps shown graphically as
(1) Obtain wT(T) vs. T elution profile from ICCD in the range from 35.0° C. to 119.0° C. with a temperature step increase of 0.200° C. Total weight fraction from 35° C. to 119° C. is normalized to 1.0 and should follow Equation 2.
(2) Calculate the median temperature (Tmedian) at cumulative weight fraction of 0.500, according to the following formula:
∫35.0T
(3) Calculate the corresponding median comonomer content in mole % (Cmedian) at the median temperature (Tmedian) by using comonomer content calibration curve according to Equation 1.
(4) Composition Distribution Breadth Index (CDBI) is defined as the total weight fraction of polymer chains with a comonomer content ranging from 0.5*Cmedian to 1.5*Cmedian from 35.0° C. to 119.0° C. Find the corresponding temperature T1 for 0.5*Cmedian and the corresponding temperature T2 for 1.5*Cmedian based on Equation 1. Composition Distribution Breadth Index (CDBI) can be obtained from the weight fraction (wT(T)) vs. temperature (T) plot between T1 and T2 as ∫T2T1wT(T)dT. If Tmedian is higher than 98.0° C., Composition Distribution Breadth Index (CDBI) is defined as 0.95;
(5) Obtain the temperature at the maximum peak height (Tp) from wT(T) vs. T profile of ICCD by searching each data point for the highest peak from 35.0° C. to 119.0° C. (if the two peaks are identical in height, then the lower temperature peak is selected); When the difference in the peak temperatures is equal to or greater than 1.1 times of the sum of full width at half maximum of each peak, the Half Width of the interpolymer composition is calculated as the arithmetic average of the full width at half maximum of each peak. If the difference in the peak temperatures is less than 1.1 times of the sum of full width at half maximum of each peak, the Half Width of the interpolymer composition is defined as the full width at half maximum of the highest temperature peak.
(6) Calculate the standard deviation of temperature (Stdev) according to the following formula:
(7) Comonomer distribution constant (CDC) is calculated from the following equation
Conventional Gel Permeation Chromatography (Conventional GPC) and MWCDI
The chromatographic system consists of a PolymerChar GPC-IR (Valencia, Spain) high temperature GPC chromatograph equipped with an internal IR5 infra-red detector (IR5). The autosampler oven compartment is set at 160° C. and the column compartment is set at 150° C. The columns used are 4 Agilent “Mixed A” 30 cm 20-micron linear mixed-bed columns. The chromatographic solvent used is 1,2,4 trichlorobenzene and contains 200 ppm of butylated hydroxytoluene (BHT). The solvent source is nitrogen sparged. The injection volume used is 200 microliters and the flow rate is 1.0 milliliter/minute.
Calibration of the GPC column set is performed with at least 20 narrow molecular weight distribution polystyrene standards with molecular weights ranging from 580 to 8,400,000 g/mol and are arranged in 6 “cocktail” mixtures with at least a decade of separation between individual molecular weights. The standards are purchased from Agilent Technologies. The polystyrene standards are prepared at 0.025 grams in 50 milliliters of solvent for molecular weights equal to or greater than 1,000,000 g/mol, and 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000 g/mol. The polystyrene standards are dissolved at 80° C. with gentle agitation for 30 minutes. The polystyrene standard peak molecular weights are converted to ethylene/alpha-olefin interpolymer molecular weights using the following equation (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)):
Mpolyethylene=A×(Mpolystyren) (Eq. 7)
where M is the molecular weight, A has a value of 0.4315 and B is equal to 1.0.
A fifth order polynomial is used to fit the respective ethylene/alpha-olefin interpolymer-equivalent calibration points. A small adjustment to A (from approximately 0.39 to 0.44) is made to correct for column resolution and band-broadening effects such that NIST standard NBS 1475 is obtained at a molecular weight of 52,000 g/mol.
The total plate count of the GPC column set is performed with Eicosane (prepared at 0.04 g in 50 milliliters of TCB and dissolved for 20 minutes with gentle agitation). The plate count (Equation 8) and symmetry (Equation 9) are measured on a 200 microliter injection according to the following equations:
where RV is the retention volume in milliliters, the peak width is in milliliters, the Peak Max is the maximum height of the peak, and half height is one half of the height of the peak maximum.
where RV is the retention volume in milliliters and the peak width is in milliliters, Peak max is the maximum position of the peak, one tenth height is one tenth of the height of the peak maximum, and where rear peak refers to the peak tail at later retention volumes than the Peak max and where front peak refers to the peak front at earlier retention volumes than the Peak max. The plate count for the chromatographic system should be greater than 22,000 and symmetry should be between 0.98 and 1.22.
Samples are prepared in a semi-automatic manner with the PolymerChar “Instrument Control” Software, wherein the samples are weight-targeted at 2 mg/ml, and the solvent (contained 200 ppm BHT) is added to a pre nitrogen-sparged septa-capped vial, via the PolymerChar high temperature autosampler. The samples are dissolved for 3 hours at 160° C. under “low speed” shaking.
The calculations of Mn(GPC), Mw(GPC), and Mz(GPC) are based on GPC results using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph according to Equations 11a-c, using PolymerChar GPCOne™ software, the baseline-subtracted IR chromatogram at each equally-spaced data collection point i (IRi) and the ethylene/alpha-olefin interpolymer equivalent molecular weight obtained from the narrow standard calibration curve for the point i (Mpolyethylene,i in g/mol) from Equation 7. Subsequently, a GPC molecular weight distribution (GPC-MWD) plot (wtGPC(lgMW) vs. lgMW plot, where wtGPC(lgMW) is the weight fraction of the interpolymer molecules with a molecular weight of lgMW) can be obtained. Molecular weight is in g/mol and wtGPC(lgMW) follows the Equation 10.
∫wtGPC(lg MW)d lg MW=1.00 (Eq. 10)
Number-average molecular weight Mn(GPC), weight-average molecular weight Mw(GPC) and z-average molecular weight Mz(GPC) can be calculated as the following equations.
In order to monitor the deviations over time, a flow rate marker (decane) is introduced into each sample via a micropump controlled with the PolymerChar GPC-IR system. This flow rate marker (FM) is used to linearly correct the pump flow rate (Flowrate(nominal)) for each sample by RV alignment of the respective decane peak within the sample (RV(FM Sample)) to that of the decane peak within the narrow standards calibration (RV(FM Calibrated)). Any changes in the time of the decane marker peak are then assumed to be related to a linear-shift in flow rate (Flowrate(effective)) for the entire run. To facilitate the highest accuracy of a RV measurement of the flow marker peak, a least-squares fitting routine is used to fit the peak of the flow marker concentration chromatogram to a quadratic equation. The first derivative of the quadratic equation is then used to solve for the true peak position. After calibrating the system based on a flow marker peak, the effective flow rate (with respect to the narrow standards calibration) is calculated as Equation 12. Processing of the flow marker peak is done via the PolymerChar GPCOne™ Software. Acceptable flow rate correction is such that the effective flowrate should be within 0.5% of the nominal flowrate.
Flow rateeffective=Flow ratenominal×(RV(FMcalibrated)/RV(FMSample)) (Eq. 12)
A calibration for the IR5 detector ratioing can be performed using at least eight ethylene/alpha-olefin interpolymer standards (one polyethylene homopolymer and seven ethylene/octene copolymers) of known short chain branching (SCB) frequency (measured by the 13C NMR Method), ranging from homopolymer (0 SCB/1000 total C) to approximately 50 SCB/1000 total C, where total C=carbons in backbone+carbons in branches. Each standard has a weight-average molecular weight from 36,000 g/mol to 126,000 g/mol, as determined by GPC. Each standard has a molecular weight distribution (Mw(GPC)/Mn(GPC)) from 2.0 to 2.5, as determined by GPC. The “IR5 Area Ratio (or “IR5 Methyl Channel Area/IR5 Measurement Channel Area”)” of “the baseline-subtracted area response of the IR5 methyl channel sensor” to “the baseline-subtracted area response of IR5 measurement channel sensor” (standard filters and filter wheel as supplied by PolymerChar:Part Number IR5_FWM01 included as part of the GPC-IR instrument) is calculated for each of the “SCB” standards. A linear fit of the SCB frequency versus the “IR5 Area Ratio” is constructed in the form of the following equation:
SCB/1000 total C=A0+[A1×(IR5Methyl Channel Area/IR5Measurement Channel Area)] (Eq.13)
where A0 is the SCB/1000 total C intercept at an “IR5 Area Ratio” of zero, and A1 is the slope of the SCB/1000 total C versus “IR5 Area Ratio” and represents the increase in the SCB/1000 total C as a function of “IR5 Area Ratio.”
A series of linear baseline-subtracted chromatographic heights for the chromatogram generated by the “IR5 methyl channel sensor” are established as a function of column elution volume, to generate a baseline-corrected chromatogram (methyl channel). A series of linear baseline-subtracted chromatographic heights for the chromatogram generated by the “IR5 measurement channel” are established as a function of column elution volume, to generate a base-line-corrected chromatogram (measurement channel).
The “IR5 Height Ratio” of “the baseline-corrected chromatogram (methyl channel)” to “the baseline-corrected chromatogram (measurement channel)” is calculated at each column elution volume index (each equally-spaced index, representing 1 data point per second at 1 ml/min elution) across the sample integration bounds. The “IR5 Height Ratio” is multiplied by the coefficient A1, and the coefficient A0 is added to this result, to produce the predicted SCB frequency of the sample. The result is converted into mole percent comonomer as follows in Equation 14:
Mole Percent Comonomer={SCBf/[SCBf+((1000−SCBf*Length of comonomer)/2)]}*100 (Eq. 14),
where “SCBf” is the “SCB per 1000 total C”, and the “Length of comonomer” is the number of carbons of the comonomer, e.g. 8 for octene, 6 for hexene, and so forth.
Each elution volume index is converted to a molecular weight value (Mwi) using the method of Williams and Ward (described above; Equation 7). The “Mole Percent Comonomer” is plotted as a function of lg(Mwi), and the slope is calculated between Mwi of 20,000 and Mwi of 200,000 g/mol (end group corrections on chain ends are omitted for this calculation). Linear regression is used to calculate the slope between, and including, Mwi from 20,000 to 200,000 g/mol, wherein the height of the concentration chromatogram (wtGPC(lgMW) vs. lgMW plot) is at least 10% of the peak height of the chromatogram. This slope is defined as the molecular weighted comonomer distribution index (MWCDI).
Zero-Shear Viscosity Ratio (ZSVR)
Zero-shear viscosity ratio is defined as the ratio of the zero-shear viscosity (ZSV) of the branched polyethylene material to the ZSV of a linear polyethylene material (see ANTEC proceeding below) at the equivalent weight average molecular weight (Mw(GPC)), according to the following equation:
The ZSV value of the interpolymer (η0B) is obtained from creep test, at 190° C., via the method described below. The Mw(GPC) value is determined by the conventional GPC method (Equation 11b), as discussed above. The correlation between ZSV of linear polyethylene (η0L) and its Mw(GPC) is established based on a series of linear polyethylene reference materials. A description for the ZSV-Mw(GPC) relationship can be found in the ANTEC proceeding: Karjala et al., Detection of Low Levels of Long-chain Branching in Polyolefins, Annual Technical Conference—Society of Plastics Engineers (2008), 66th 887-891.
Creep Test
The ZSV value of the interpolymer (η0B) is obtained from a constant stress rheometer creep test at 190° C. in a nitrogen environment using DHR, TA Instrument. The samples are subjected to flow between two 25 mm diameter plate fixtures positioned parallel to each other. Samples are prepared by compression molding pellets of the interpolymer into circular plaques of about 1.5-2.0 mm thick. The plaques are further cut into 25 mm diameter disks and sandwiched between the plate fixtures of the TA Instrument. The oven on the TA instrument is closed for 5 minutes after sample loading and before setting the gap between the plate fixtures to 1.5 mm, opening the oven to trim the edges of the sample, and reclosing the oven. A logarithmic frequency sweep between 0.1 to 100 radians/second at 190° C., 300 seconds of soak time, and 10% strain is conducted before and after the creep test to determine whether the sample has degraded. A constant low shear stress of 20 Pa is applied for all of the samples, to ensure that the steady state shear rate is low enough to be in the Newtonian region. Steady state is determined by taking a linear regression for the data in the last 10% time window of the plot of “lg (J(t)) vs. lg(t)”, where J(t) is creep compliance and t is creep time. If the slope of the linear regression is greater than 0.97, steady state is considered to be reached, then the creep test is stopped. In all cases in this study, the slope meets the criterion within one hour. The steady state shear rate is determined from the slope of the linear regression of all of the data points, in the last 10% time window of the plot of “ε vs. t”, where ε is strain. The zero-shear viscosity is determined from the ratio of the applied stress to the steady state shear rate.
1H NMR Method
A stock solution (3.26 g) is added to 0.133 g of the polymer sample in 10 mm NMR tube. The stock solution is a mixture of tetrachloroethane-d2 (TCE) and perchloroethylene (50:50 in weight) 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 periodic vortex mixing. The samples are free of the additives that may contribute to unsaturation, for example, slip agents such as erucamide. Each 1H NMR analysis is run with a 10 mm cryoprobe, at 120° C., on Bruker AVANCE 400 MHz spectrometer.
Two experiments are run to measure unsaturation: one control and one double presaturation experiment. For the control experiment, the data are processed with an exponential window function with 1 Hz line broadening and the baseline is corrected from about 7 to −2 ppm. The signal from residual 1H of TCE is set to 100, the integral (Itotal) from about −0.5 to 3 ppm is used as the signal from the whole polymer in the control experiment. The number of total carbons, NC, in the polymer is calculated as follows in Equation 16:
NC=Itotal/2 (Eq. 16)
For the double presaturation experiment, the data are processed with an exponential window function with 1 Hz line broadening, and the baseline is corrected from about 6.6 to 4.5 ppm. The signal from residual 1H of TCE is set to 100, and the corresponding integrals for unsaturations (Ivinylene, Itrisubstituted, Ivinyl and Ivinylidene) are integrated. It is well known to use NMR spectroscopic methods for determining polyethylene unsaturation, for example see Busico, V., et al., Macromolecules, 2005, 38, 6988. The number of unsaturation unit for vinylene, trisubstituted, vinyl and vinylidene are calculated as follows:
Nvinylene=Ivinylene/2 (Eq. 17),
Ntrisubstituted=Itrisubstitute (Eq. 18),
Nvinyl=Ivinyl/2 (Eq. 19),
Nvinylidene=Ivinylidene/2 (Eq. 20).
The unsaturation units per 1,000 total carbons, i.e., all polymer carbons including backbone and branches, are calculated as:
Nvinylene/1,000C=(Nvinylene/NC)*1,000 (Eq. 21),
Ntrisubstituted/1,000C=(Ntrisubstituted/NC)*1,000 (Eq. 22),
Nvinyl/1,000C=(Nvinyl/NCH2)*1,000 (Eq. 23),
Nvinylidene/1,000C=(Nvinylidene/NC)*1,000 (Eq. 24).
The chemical shift reference is set at 6.0 ppm for the 1H signal from residual proton from TCE-d2. The control is run with a ZG pulse, NS=4, DS=12, SWH=10,000 Hz, AQ=1.64s, D1=14s. The double presaturation experiment is run with a modified pulse sequence, with O1P=1.354 ppm, 02P=0.960 ppm, PL9=57 db, PL21=70 db, NS=100, DS=4, SWH=10,000 Hz, AQ=1.64 s, D1=1 s (where D1 is the presaturation time), D13=13 s.
13C NMR Method
The samples are prepared by adding approximately 3 g of a 50/50 mixture of tetrachloroethane-d2/orthodichlorobenzene, containing 0.025 M Cr(AcAc)3, to a 0.25 g polymer sample in a Norell 1001-7 10 mm NMR tube. Oxygen is removed from the sample by purging the tube headspace with nitrogen. The samples are then dissolved and homogenized by heating the tube and its contents to 150° C. using a heating block and heat gun. Each sample is visually inspected to ensure homogeneity. Samples are thoroughly mixed immediately prior to analysis, and are not allowed to cool before insertion into the heated NMR probe. This is necessary to ensure the sample is homogeneous and representative of the whole. All data are collected using a Bruker 400 MHz spectrometer equipped with a Bruker cryoprobe. The data are acquired using a 6 second pulse repetition delay, 90-degree flip angles, and inverse gated decoupling with a sample temperature of 120° C. All measurements are made on non-spinning samples in locked mode. Samples are allowed to thermally equilibrate for 7 minutes prior to data acquisition. The 13C NMR chemical shifts are internally referenced to the EEE triad at 30 ppm.
C13 NMR comonomer Content: It is well known to use NMR spectroscopic methods for determining polymer composition. ASTM D 5017-96; J. C. Randall et al., in “NMR and Macromolecules” ACS Symposium series 247; J. C. Randall, Ed., Am. Chem. Soc., Washington, D.C., 1984, Ch. 9; and J. C. Randall in “Polymer Sequence Determination”, Academic Press, New York (1977) provide general methods of polymer analysis by NMR spectroscopy.
Denier Measurement
Fiber size is measured via optical microscopy. Denier (defined as the weight of such fiber for 9000 meter) is calculated based on the density of each polymer component and fiber size.
2% Secant Modulus (E) and Yield Stress (a)
Yield stress and 2% secant modulus are measured as follows: Specimens are injection molded according to ASTM D3641, using a Hitachi Toyo Si-90 Plastar Injection Molding Machine. It is equipped with a 1.1 inch diameter screw (i.e. 28 mm), and has a clamping force of 90 U.S. Tons. The temperature profile was set at 48° C./121° C./175° C./204° C./204° C. from throat to nozzle. The melt temperature was 200° C. The injection pressure was 2000 bar with an injection time of 1.43 seconds. The injection speed was 40 mm/s. The hold pressure was set at 300 bar and the hold time was 25 seconds. The cooling time was 20 seconds and recovery time was 12.49 seconds for PE and 9.84 seconds for PP. The screw speed was 90 rpm.
Tensile test is performed in accordance with the ASTM D638 testing procedure on injection molded Type I ASTM bars at 2 inch/minute tensile speed and at room temperature. Yield stress (σy) and 2% secant modulus (E) are obtained from the tensile stress-strain curve. 2% secant modulus is defined as E=stress at 2% strain/2%. Yield stress is the highest stress in the range of 0% strain to 50% strain on the stress-strain curve. Five specimens were measured and the average values were reported.
Curl
Curl is measured via optical microscopy. Curl (defined as the curvature of the fibers) is calculated as the inverse of the radius of the approximate helix formed by fiber. This is equal to the radius of the circle formed by projection of the approximate helix formed by the fiber on a surface perpendicular to it. Average value of at least 5 samples is reported.
Materials used:
All raw materials (ethylene monomer and 1-octene comonomer) and the process solvent (a narrow boiling range high-purity isoparaffinic solvent, product name Isopar-E commercially available from ExxonMobil Chemical) are purified with molecular sieves before introduction into the reaction environment. Hydrogen is supplied pressurized as a high purity grade and is not further purified. The reactor ethylene feed stream is pressurized via a mechanical compressor to above reaction pressure. The solvent and comonomer feed is pressurized via a pump to above reaction pressure. The individual catalyst components are manually batch diluted to suitable component concentrations with purified solvent and pressured to above reaction pressure. All reaction feed flows are measured with mass flow meters and independently controlled with computer automated valve control systems.
A two reactor system is used in a series configuration. Each continuous solution polymerization reactor consists of a liquid full, non-adiabatic, isothermal, circulating, loop reactor which mimics a continuously stirred tank reactor (CSTR) with heat removal. Independent control of all fresh solvent, ethylene, hydrogen, and catalyst component feeds is possible. The total fresh feed stream to each reactor (solvent, ethylene, 1-octene, and hydrogen) is temperature controlled to maintain a single solution phase by passing the feed stream through a heat exchanger. The total fresh feed to each polymerization reactor is injected into the reactor at two locations with approximately equal reactor volumes between each injection location. The fresh feed is controlled with each injector receiving half of the total fresh feed mass flow. The catalyst components are injected into the polymerization reactor through a specially designed injection stingers. The primary catalyst (pre-catalyst) component feed is computer controlled to maintain each reactor ethylene conversion at the specified targets. The cocatalyst components are fed based on calculated specified molar ratios to the primary catalyst (pre-catalyst) component. Immediately following each reactor feed injection location, the feed streams are mixed with the circulating polymerization reactor contents with static mixing elements. The contents of each reactor are continuously circulated through heat exchangers responsible for removing much of the heat of reaction and with the temperature of the coolant side responsible for maintaining an isothermal reaction environment at the specified temperature. Circulation around each reactor loop is provided by a pump.
In dual series reactor configuration the effluent from the first polymerization reactor (containing solvent, ethylene, 1-octene, hydrogen, catalyst components, and polymer) exits the first reactor loop and is added to the second reactor loop.
The second reactor effluent enters a zone where it is deactivated with the addition of and reaction with water. Following catalyst deactivation and additive addition, the reactor effluent enters a devolatization system where the polymer is removed from the non-polymer stream. The isolated polymer melt is pelletized and collected. The non-polymer stream passes through various pieces of equipment which separate most of the ethylene which is removed from the system. Most of the solvent and unreacted 1-octene is recycled back to the reactor after passing through a purification system. A small amount of solvent and 1-octene is purged from the process.
The reactor stream feed data flows that correspond to the values in Table 2 used to produce the examples. The data are presented such that the complexity of the solvent recycle system is accounted for and the reaction system can be treated more simply as a once through flow diagram. Catalyst components used are referenced in Table 3.
Each of the polymers made was tested for various properties according to the methods set forth above. Results are shown in Table 4.
Bicomponent fibers having a highly eccentric core sheath configuration were made with the Exxon 3854 PP core and one of the ethylene copolymers as the sheath. The fibers were spun on the Hills Line according to the following conditions. Extruder profiles are adjusted to achieve a melt temperature of 240° C. Throughput rate is 0.6 ghm (gram per hole per minute). A Hills Bicomponent die is used operating at a 40/60 core/sheath weight ratio with Exxon 3854 PP in one extruder and the ethylene copolymer in another extruder. The die configuration consists of 144 holes, with a hole diameter of 0.6 mm and a length/diameter (L/D) of 4/1. Quench air temperature and flow rate are set at 23° C., and 520 cfm (cubic feet per minute). After the quenching zone, a draw tension is applied on the 144 filaments by pneumatically entraining the filaments in a slot unit with an air stream. Velocity of the air stream is controlled by the slot aspirator pressure and the slot aspirator pressure is set at 20 psi.
The obtained fibers were stretched at room temperature using an Instron tensile machine to 50% elongation at a stretch rate of 100%/min. Then the stretched fibers were released from the Instron and relaxed before curvature was measured. The results are shown in Table 5.
Bicomponent fibers were made having a polyproplylene core and a sheath (having a concentric core-sheath geometry). The sheath material was ASPUN™ 6835, or Sample 1, or Sample 2. Fibers are spun on a Hills Bicomponent Continuous Filament Fiber Spinning Line at a throughput rate of 0.5 ghm (grams per hole per minute). A Hills Bicomponent die is used operating at a 40/60 core/sheath ratio in weight with Exxon 3854 PP in one extruder and the ethylene/alpha-olefin intercopolymer in another extruder. The hole diameter used was 0.5 mm and length/diameter L/D was 4/1. Quench air temperature and flow rate are set at 25° C., and 520 cfm (cubic feet per minute). Extruder profiles are adjusted to achieve a melt temperature of 240° C. After the quenching zone, The 144 fibers are collected by the denier roll and then guided to two stretch rolls. The two stretch rolls are rotating at different speeds and fibers are stretched between them. After the fibers are stretched, they are wrapped around a bobbin. Thereafter, the fibers were unwrapped from the bobbin before examined for curl under microscope. Fiber spinning conditions are shown in Table 6. Curvature results are shown in Table 7.
This application is a National Stage application of PCT/US2019/062337, filed Nov. 20, 2019, which claims benefit of U.S. Application No. 62/769,618 filed on Nov. 20, 2018, both of which are incorporated by reference herein in their entirety.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US2019/062337 | 11/20/2019 | WO |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2020/106798 | 5/28/2020 | WO | A |
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| Number | Date | Country | |
|---|---|---|---|
| 20220228297 A1 | Jul 2022 | US |
| Number | Date | Country | |
|---|---|---|---|
| 62769618 | Nov 2018 | US |
