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    • 专利摘要:
    polymeric mixtures and films made from them. the present invention relates to polymeric mixing and films made therefrom are provided. the polymeric mixture can include a first polyethylene having a density of less than about 0.940 g / cm³, a melt index (<sym>) greater than 0.75 g / 10 min and a melt index ratio (<sym > / <sym>) of less than 30. the polymeric mixture can also include a second polyethylene having a density of less than about 0.940 g / cm, a melt index (<sym>) of less than 1g / 10 min, a ratio of fusion index (<sym> / <sym>) greater than 30 and a molecular weight distribution (mw / mn) of less than 4.5.
    公开号:BR112012025925B1
    申请号:R112012025925-3
    申请日:2011-03-22
    公开日:2020-03-17
    发明作者:Ching-Tai Lue；Christopher R. Davey
    申请人:Univation Technologies, Llc；
    IPC主号:
    专利说明:

    "POLYMERIC MIXTURE AND FILM" BACKGROUND
    [001] Stretch films are widely used in a variety of packaging and packaging applications, for example, packaging of goods for transportation and storage. Stretch films or sticky stretch films having high adhesion properties are particularly useful because the high adhesion helps to prevent the film from shedding from the packaged goods. As the film is stretched, however, localized deformation can result in a large fluctuation on elongation, giving rise to weaker and more elongated film bands across the direction of stretching, a defect known as "tiger streak formation". In addition, the formation of tiger stripes is usually accompanied by a decrease in adherence, which is undesirable.
    [002] To impart adhesion properties or enhance the adhesion properties of a particular film, a number of techniques have been used, including the addition of adhesion additives or "adhesives". Such adhesives include polybutenes, low molecular weight polyisobutylene (PIB), polyiterpenes, amorphous polypropylene, copolymers of ethylene vinyl acetate, microcrystalline wax, alkali metal sulfosuccinates and fatty acid mono- and diglycerides. Current stretch films, however, still exhibit tiger streak formation and undesirable losses in grip when drawn.
    [003] There is a need, therefore, for improved sticky stretch films having improved grip after stretching and / or having reduced or no tiger streak formation during stretching of the film.
    SUMMARY
    [004] Polymeric mixtures and films made from them are provided. The polymeric mixture can include a first polyethylene having a density of less than about 0.940 g / cm3, a melt index (I2) greater than 0.75 g / 10 min and a melt index ratio (I21 / I2) less than 30. In some embodiments, the first polyethylene has a density in the range of about 0.915 g / cm g / cm3 to about 0.940 g / cm3, a melting index (I2) of about 0.75 g / 10 min to about 20 ° C and a melt index (I21 / I2) ratio of about 20 to about 30. The polymeric mixture can also include a second polyethylene having a density of less than about 0.940 g / cm, a melt index (I2) of less than 1g / 10 min, a melt index ratio (I21 / I2) greater than 30 and a molecular weight distribution (Mw / Mn) of less than 4 , 5. In some embodiments, the second polyethylene can have a density of about 0.915 g / cm3 to about 0.940 g / cm, a melt index (I2) of about 0.01 g / 10 min to about 0.9 g / 10 min, a melt index ratio (I21 / I2) of about 30 to about 100 and a molecular weight distribution (Mw / Mn) of about 3 to about 4.5.
    [005] Also described are methods for making the polymeric mixture. The method may comprise mixing the first polyethylene with the second polyethylene under conditions sufficient to produce a mixture of polyethylene.
    DETAILED DESCRIPTION
    [006] It has been found that stretch films made from a polymeric mixture comprising two or more polyethylene, as discussed and described here, can have improved properties, including an applicability over a wide range of stretch ratios, without suffering from localized deformation that leads the formation of tiger stripes. In fact, surprisingly and unexpectedly, it has been found that the occurrence of tiger streak formation in stretch films made of a first polyethylene having a density of less than about 0.940 g / cm3, a melting index (I2) of about 0.75 g / 10 min at about 20 g / 10 min and a melt index ratio (I21 / I2) of less than 30 can be eliminated by mixing the first polyethylene with another polyethylene ("second polyethylene") having a melt index (I2) of less than 1 g / 10 min, a melt index ratio (I21 / I2) greater than 30 and a molecular weight distribution (Mw / Mn) of less than 4.5. In addition, surprisingly and unexpectedly as well, that films made of a polymeric mixture having the first polyethylene and the second polyethylene can have improved adhesion properties before stretching, after stretching or both.
    [007] The term "polyethylene" refers to a polymer having at least 50% by weight of ethylene-derived units, preferably at least 70% by weight of ethylene-derived units, more preferably at least 80% by weight of ethylene-derived units. ethylene-derived units or 90% by weight of ethylene-derived units or 95% by weight of ethylene-derived units or 100% by weight of ethylene-derived units. The first and second polyethylenes can thus be homopolymers or copolymers, including a terpolymer, having one or more other monomer units or any combination thereof. As such, the first polyethylene and / or the second polyethylene can include, for example, one or more of other olefin (s) and / or α-olefin comonomer (s). Illustrative α-olefin comonomers may include, but are not limited to, those having from 3 to about 20 carbon atoms, such as C3-C20 α-olefins, C3-C12 α-olefins or C3C8 α-olefins. Suitable α-olefin comonomers can be linear or branched or can include two unsaturated carbon-carbon bonds (dienes). Two or more comonomers can be used. Examples of suitable comonomers can include, but are not limited to, linear C3-C12 α-olefins and α-olefins having one or more C1-C3 alkyl branches or an aryl group.
    [008] Examples of useful comonomers include propylene; 1-butene; 3-methyl-1-butene; 3,3-dimethyl-1-butene; 1-pentene; 1-pentene with one or more methyl, ethyl or propyl substituents; 1-hexene; 1-hexene with one or more methyl, ethyl or propyl substituents; 1-heptene; 1-heptene with one or more methyl, ethyl or propyl substituents; 1-octene; 1-octene with one or more methyl, ethyl or propyl substituents; 1-nonene; 1-nonene with one or more methyl, ethyl or propyl substituents; ethyl, methyl- or dimethyl-substituted 1-decene; 1-dodecene; and styrene; and combinations thereof. Preferred comonomers include 1-butene, 1-hexene and 1-octene.
    [009] If one or more comonomers are used, the monomer, i.e. ethylene, can be polymerized in a proportion of about 50% by weight to about 99.9% by weight of monomer or about 70% by weight of about 99% by weight of monomer or about 80% by weight of about 98% by weight of monomer, with from about 0.1% by weight to about 50% by weight of one or more comonomers or from about 1% by weight to about 30% by weight of one or more comonomers or from about 2% by weight to about 20% by weight of one or more comonomers. If one or more comonomers are present in either or both of the first polyethylene and the second polyethylene, the amount of one or more comonomers in the first polyethylene and the second polyethylene can be the same or different. For example, the first polyethylene can have a comonomer concentration ranging from about 10% by weight to about 20% by weight and the second polyethylene can have a comonomer concentration ranging from about 2% by weight to about 10% by weight. The comonomer (s) in particular, if present, in the first polyethylene and the second polyethylene may be the same or different (s). For example, the first polyethylene and the second polyethylene can both include 1-hexene as the comonomer. In another example, the first polyethylene can include 1-hexene as the comonomer and the second polyethylene can 1-butene as the comonomer.
    [010] The first polyethylene can be mixed with one or more second polyethylene to produce a polymeric mixture. The first polyethylene can be distinguished from the second polyethylene by differing in at least one property or characteristic. For example, the first polyethylene can be distinguished from the second polyethylene in that it has a different melt index (I2), molecular weight distribution (MWD), different melt index ratio (I21 / I2) or any combination thereof. In another example, the first polyethylene may be a linear low density polyethylene (Linear Low Density Polyethylene - LLDPE) and the second polyethylene may be a low density polyethylene (Low Density Polyethylene -LDPE). LDPE can also be referred to as "branched" or "heterogeneously branched" polyethylene because of the relatively large number of long chain branches extending from the polymeric main part. Unlike LDPE, LLDPE is a linear polyethylene and does not contain long chain branching. As such, the first polyethylene can be a linear polyethylene, i.e., without long chain branching and the second polyethylene can include long chain branching.
    [011] The first polyethylene can have a density of about 0.890 g / cm3 to about 0.940 g / cm3. For example, the first polyethylene can have a density ranging from a low of about 0.910 g / cm3, about 0.912 g / cm3 or about 0.915 g / cm3 to a high of about 0.930 g / cm3, about 0.935 g / cm3 or about 0.940 g / cm3. The first polyethylene can have a density of about 0.915 g / cm3 to about 0.935 g / cm3 or about 0.915 g / cm3 to about 0.930 g / cm3 or about 0.915 g / cm3 to about 0.925 g / cm3 or about 0.916 g / cm3 to about 0.924 g / cm3 or about 0.917 g / cm3 to about 0.923 g / cm3 or about 0.918 g / cm3 to about 0.922 g / cm3. Density is a physical property of a composition and can be determined in accordance with ASTM D-792.
    [012] The second polyethylene can have a density of less than about 0.940 g / cm3. The second polyethylene can have a density ranging from a low of about 0.900 g / cm3, about 0.905 g / cm3 or about 0.910 g / cm3 to a high of about 0.920 g / cm3, about from 0.999 g / cm3, about 0.930 g / cm3 or about 0.935 g / cm3. For example, the second polyethylene can have a density ranging from a low of about 0.915 g / cm3, about 0.917 g / cm3 or about 0.918 g / cm3 to a high of about 0.920 g / cm3, about 0.922 g / cm3, about 0.925 g / cm3 or about 0.927 g / cm3. The second polyethylene can have a density of about 0.915 g / cm3 to about 0.935 g / cm3 or about 0.915 g / cm3 to about 0.930 g / cm3 or about 0.915 g / cm3 to about 0.925 g / cm3 or about 0.916 g / cm3 to about 0.924 g / cm3 or about 0.917 g / cm3 to about 0.923 g / cm3 or about 0.918 g / cm3 to about 0.922 g / cm3 [013] "molecular weight distribution" means the same thing as the PolyDispersity Index (PDI). The molecular weight distribution (PDI) is the ratio of average molecular weight (Mw) to the average numerical molecular weight (Mn), that is, Mw / Mn.
    [014] Mw, Mn and Mz can be measured using gel permeation chromatography (Gel Permeation Chromatography - GPC) is also known as size exclusion chromatography (SEC). This technique uses an instrument containing columns packed with porous globules, an elution solvent and detector in order to separate polymeric molecules of different sizes. The measurement of molecular weight by means of SEC is a well-known technique and is discussed in more detail, for example, in Slade, P. E.
    Ed., Polymer Molecular Weights Part II, Marcel Dekker, Inc., NY, (1975) 287-368; Rodriguez, F., Principles of Polymer Systems, 3rd ed., Hemisphere Pub. Corp., NY, (1989) 155-160;
    U.S. Patent No. 4,540,753; and Verstrate et al., Macromolecules, vol. 21, (1988) 3360; T. Sun et al., Macromolecules, Vol. 34, (2001) 6812-6820.
    [015] The first polyethylene can have a molecular weight distribution (Mw / Mn) of about 3.5 to about 5.5. For example, the first polyethylene may have a molecular weight distribution (Mw / Mn) ranging from a low of about 3.5, about 3.7 or about 4 to a high of about 5, about 5, 25 or about 5.5. The first polyethylene can have a molecular weight distribution (Mw / Mn) of about 3.6 to about 5.4, about 3.8 to about 5.1, or about 3.9 to about 4, 9.
    [016] The second polyethylene may have a molecular weight distribution (Mw / Mn) of less than about 4.5, preferably less than about 4.3 or 4.1 or 4 or 3.9 or 3, 8 or 3.7 or 3.6 or 3.5. For example, the second polyethylene may have a molecular weight distribution (Mw / Mn) ranging from a low of about 3.0, about 3.1, about 3.2 or about 3.3 to a high of about 4, about 4.1, about 4.2 or about 4.3. The molecular weight distribution (Mw / Mn) of the composition of the second polyethylene can range from about 3.0 to about 4.5, from about 3.2 to about 4, from about 3.2 to about 3, 9 or from about 3.2 to about 3.7.
    [017] The first polyethylene can have a melt index (MI) or (I2) of about 0.75 g / 10 min to about 20 g / 10 min. MI (I2) is measured according to ASTM D-1238-E (at 190 ° C, weight of 2.16 kg). The first polyethylene can have an MI (I2) ranging from about 0.75 g / 10 min to about 15 g / 10 min, about 0.85 g / 10 min to about 10 g / 10 min or about 0.9 g / 10 min to about 8 g / 10 min. For example, the first polyethylene may have an MI (I2) ranging from a low of about 0.75 g / 10 min, about 1 g / 10 min or about 2 g / 10 min to a high of about 3 g / 10 min, about 4 g / 10 min or about 5 g / 10 min. For example, the first polyethylene may have an MI (I2) of about 0.75 g / 10 min to about 6 g / 10 min, about 1 g / 10 min to about 8 g / 10 min, about 0.8 g / 10 min to about 6 g / 10 min or about 1 g / 10 min to about 4.5 g / 10 min. In another example, the first polyethylene may have an MI (I2) greater than 1 g / 10 min.
    [018] The second polyethylene can have an MI (I2) of less than 1 g / 10 min. The second polyethylene can have an MI (I2) of less than about 0.9 g / 10 min, of less than about 0.8 g / 10 min, of less than about 0.7 g / 10 min, of less than about 0.6 g / 10 min, less than about 0.5 g / 10 min, less than about 0.4 g / 10 min, less than about 0.3 g / 10 min , less than about 0.2 g / 10 min or less than about 0.1 g / 10 min. The second polyethylene may have an MI (I2) oscillating from a low of about 0.01 g / 10 min, about 0.05 g / 10 min, about 0.1 g / 10 min, about 0.2 g / 10 min or about 0.3 g / 10 min at a high of about 0.5 g / 10 min, about 0.6 g / 10 min, about 0.7 g / 10 min, about 0 , 8 g / 10 min or about 0.9 g / 10 min. For example, the second polyethylene can have an MI (I2) of about 0.01 g / 10 min to about 0.6 g / 10 min, about 0.1 g / 10 min to about 0.7 g / 10 min, about 0.2 g / 10 min to about 0.75 g / 10 min or about 0.1 g / 10 min to about 0.5 g / 10 min.
    [019] The terms "fusion index ratio," "MIR," and "I21 / I2," are used interchangeably and refer to the flow index ratio (Flow Index - FI) or (I21) to MI ( I2). FI (I21) is measured according to ASTM D-1238-F (at 190 ° C, weight 21.6 kg). The first polyethylene can have an MIR (I21 / I2) of less than 30. The first polyethylene can have an MIR ranging from a low of about 20, about 22 or about 24 to a high of about 25, about 26, about 27, about 28, about 29 or about 30. For example, the first polyethylene can have an MIR ranging from about 20 to about 30 or about 22 to about 28 or about 24 to about 28.
    [020] The second polyethylene can have an MIR of more than 30. The second polyethylene can have an MIR of more than about 30.1, 30.5, 31, 32, 33, 34 or 35. The second polyethylene can have an MIR oscillating from a low of about 30.5, about 33 or about 35 to a high of about 100, about 150 or about 200. The second polyethylene can have an MIR ranging from a low of about 31, about 32, about 34 or about 36 to a high of about 50, about 70, about 80, about 90 or about 95. In at least one specific example, the second polyethylene can have a MIR of more than 30 to about 50 or about 33 to about 47 or about 35 to about 45.
    [021] The first polyethylene can have a molecular weight distribution (Mw / Mn) ranging from about 3.5 to about 5.5 and an MIR of less than 30 and the second polyethylene can have a molecular weight distribution ( Mw / Mn) oscillating from about 3 to about 4.5 and an MIR of more than 30. The first polyethylene can have an Mw / Mn oscillating from about 4 to about 5.5 and an MIR of less than 30 and the second polyethylene can have an Mw / Mn ranging from about 3 to about 4 and an MIR of more than 30. The first polyethylene can have an Mw / Mn greater than 4 and up to about 5.5 and an MIR less than 30 and the second polyethylene can have an Mw / Mn of less than 4 and an MIR of more than 30. The first polyethylene can have an Mw / Mn ranging from about 4.1 to about 5.5 and a MIR of about 20 to about 29 and the second polyethylene can have an Mw / Mn ranging from about 3 to about 4 and an MIR of about 31 to about 100.
    [022] The first polyethylene can have a hexane extractable content of about 0.3% to about 5.5%. The second polyethylene can have a hexane extractable content of less than about 5%, less than about 4%, less than about 3%, less than about 2.5%, less than about 2%, less than about 1.8%, less than about 1.5%, less than about 1.3% or less than about 1%. For example, the second polyethylene may have a hexane extractable content of less than about 0.9%, less than about 0.7%, less than about 0.5% or less than about 0 , 3%. The amount of hexane extractables in the first polyethylene, the second polyethylene and the polymer mixture can be determined according to the FDA method (see 21 CFR § 177.1520, as revised on April 1, 2005 for details on the FDA method and requirements for contact with food, repeated and while cooked). As such, a polymeric mixture comprising the first polyethylene and the second polyethylene can have a hexane extractable content of less than about 3%, less than about 2.5%, less than about 2%, less about 1.8%, less than about 1.5%, less than about 1.3% or less than about 1%.
    [023] Although the components of the polymeric mixture, that is, the first polyethylene and the second polyethylene, have been discussed as unique polyethylene, mixtures of two or more of such first polyethylene and / or second polyethylene having the properties discussed and described here may be used. In other words, the first polyethylene may include two or more first polyethylene that differ from each other, but both have the properties discussed and described above in reference to the first polyethylene that differentiate the first polyethylene from the second polyethylene. Similarly, the second polyethylene may include two or more second polyethylene that differ from each other, but have both the properties discussed and described above that differentiate the second polyethylene from the first polyethylene.
    [024] Other illustrative polyethylenes that can be mixed with the first polyethylene and / or the second polyethylene, depending on their particular properties, may include, but are not limited to, Very Low Density Polyethylene - VLDPE) , LDPEs, LLDPEs and medium density polyethylene (Medium Density Polyethylene - MDPE). Very low density polyethylene (VLDPE) is a subset of LLDPE. VLDPEs can be produced through a series of different processes that provide polymers of different properties, but can, in general, be described as polyethylenes having a density, typically, from 0.890 or 0.900 g / cm3 to less than 0.915 g / cm3. Linear polyethylene of relatively higher density, typically in the range of 0.930 g / cm3 to 0.945 g / cm3, although often considered to be within the scope of LDPE, can also be referred to as "medium density polyethylene" (MDPE).
    Mixing Preparation [025] The polymeric mixture can be formed using conventional equipment and methods, such as by dry mixing the individual components and subsequently mixing by melting in a mixer or by mixing the components together directly in a mixer such as, for example, a Banbury mixer, a Haake mixer, a Brabender internal mixer or a single or double screw extruder, which can include a composition extruder and a single arm extruder used directly downstream from a polymerization process. A mixture or composition of the first and second polyethylenes can be indicated by the uniformity of the composition's morphology. In another example, the polymeric mixture can be produced in situ using a multi-stage polymerization reactor configuration and process. In a multistage reactor configuration, two or more reactors can be connected in series where a mixture of a first polymer and catalyst precursor can be transferred from a first reactor to a second reactor, where a second polymer can be produced and mixed in situ with the first polymer. A multi-stage polymerization reactor and methods for using it can be similar as discussed and described in U.S. Patent No. 5,677,375, for example.
    [026] The polymeric mixture can include at least 0.1 weight percent (% by weight) and up to 99.9% by weight of the first polyethylene and at least 0.1% by weight and up to 99.9% in weight of the second polyethylene, based on the total weight of the first polyethylene and the second polyethylene. The amount of the second polyethylene in the polymer mixture can range from a drop of about 5% by weight, about 10% by weight, about 20% by weight, about 30% by weight or about 40% by weight of an increase of about 60% by weight of, about 70% by weight of, about 80% by weight of, about 90% by weight of or about 95% by weight of, based on weight total of the first polyethylene and the second polyethylene. For example, the amount of the second polyethylene in the polymer mixture can range from about 15% by weight to about 40% by weight, about 10% by weight to about 35% by weight or about 20% by weight of about 45% by weight of, based on the total weight of the first polyethylene and the second polyethylene. In another example, the amount of the second polyethylene in the polymer mixture can be at least 5% by weight, at least 10% by weight, at least 15% by weight, at least 20% by weight, at least 25% by weight of at least 30% by weight of or at least 35% by weight of and less than about 50% by weight of, based on the total weight of the first and second polyethylene. The polymeric mixture can include from about 20% by weight to about 35% by weight of the second polyethylene and from about 65% by weight to about 80% by weight of the first polyethylene, based on the total weight of the first and second polyethylene.
    Final Uses [027] The polymeric mixture that includes the first polyethylene and the second polyethylene can be used for any series of applications. The polymeric mixture can be used alone or in combination with one or more other polymers, mixtures of polymers and the like, to produce a product for end use. Exemplary end uses may include, but are not limited to, films, film based products, disposable diaper liner sheets, household foil, wire and cable liner compositions, articles formed using molding techniques, for example , injection or blow molding, extrusion coating, foaming, casting and combinations thereof. End uses may also include products made from films, for example, bags, packaging films and personal products, bags, medical products such as, for example, medical films and IV bags. For end uses that include films, either or both surfaces of films produced from the polyethylene mixture can be modified using known and conventional post-forming techniques, such as corona discharge, chemical treatment, flame treatment and the like .
    [028] Films for specific end use may include, for example, stretch films. Stretch films or illustrative stretch-type films may include, but are not limited to, sticky stretch films, hand-wound stretch films and machine-stretch films. Other types of films may include, but are not limited to, retractable films, retractable roll-up films, green household films, laminates and laminated films. Films can be prepared using any conventional technique known to those skilled in the field such as, for example, techniques used to prepare stretch and / or shrink and / or blown, extruded or cast films (including shrink-over-shrink applications) . The term "stretch film" refers to films capable of stretching and applying a packaging force and includes films stretched at the time of application, as well as "pre-stretched" films, that is, films which are supplied in a form pre-stretched for use without additional stretching. Films can be monolayer films or films with multiple layers.
    Additives [029] A variety of additives can be used in the adhesive mix formulations described here, depending on the performance characteristics required by a particular application. Additives can be included in the polymeric mixture, in one or more components of the polymeric mixture, for example, the first polyethylene and / or the second polyethylene and / or in a product formed from the polymeric mixture, such as a film, as desired . The polymeric mixtures discussed and described here can include from about 0.1% by weight to about 40% by weight of additives or from about 5% by weight to about 25% by weight of additives, based on the total weight of the overall polymeric mixture.
    [030] Examples of such additives include, but are not limited to, adhesives, waxes, functionalized polymers, such as acid-modified polyolefins and / or anhydride-modified polyolefins, antioxidants (for example, hindered phenolics, such as IRGANOX® 1010 or IRGANOX® 1076 available from Ciba-Geigy) (eg IRGAFOS® 168 available from Ciba-Geigy), oils, compatibility agents, fillers, adjuvants, adhesion promoters, plasticizers, low molecular weight polymers, blocking agents, agents anti-blocking agents, antistatic agents, release agents, non-stick additives, dyes, dyes, pigments, processing aids, UV stabilizers, thermal stabilizers, neutralizers, lubricants, surfactants, nucleating agents, flexibilizers, rubbers, optical brighteners, dyes, diluents, viscosity modifiers, oxidized polyolefins and any combination thereof. Additives can be combined with one or both of the first or second polyethylene and / or can be combined with the mixture of the first and second polyethylene as other individual components, in master batches or in any combination thereof.
    [031] For applications with stretch film, an additive, such as an adhesive, can be used in one or more layers to provide adherent strength. Illustrative adhesives include any known adhesive effective to impart and / or enhance adhesion strength such as, for example, polybutenes, low molecular weight polyisobutylene (PIB), polyiterpenes, amorphous polypropylene, ethylene vinyl acetate copolymers, microcrystalline wax , alkali metal sulfosuccinates and fatty acid mono- and diglycerides, such as glycerol monostearate, glycerol mono-oleate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan mono-oleate, hydrocarbon resins and any combination of hydrocarbons and any of the same. The adhesive, if used, can be used in any concentration which will have an impact on the desired bond strength, typically 0.1 to 20% by weight or 0.25 to 6.0% by weight. Adhesive (s) can be used in monolayer films or in films with multiple layers. In multi-layer films, one or more adhesives can be added to both outer layers to provide a stretch film having two adherent sides or on just one outer layer to provide a stretch film having an adherent side.
    [032] In one example, monolayer films can be prepared from the polymeric mixture. In another example, films with multiple layers can be prepared from the polymeric mixture or mixtures thereof. Multilayer films can include one or more layers of film made of polymers other than the polymeric mixture comprising the first polyethylene and the second polyethylene. Monolayer films and / or at least one layer of a multilayer film can include the polymeric mixture, i.e., the polymeric mixture comprising the first polyethylene and the second polyethylene.
    [033] Films can be formed using any number of well-known extrusion or coextrusion techniques. Any of the commonly used blowing film, drying or melting film techniques are suitable. Films can be non-oriented, uniaxially oriented or biaxially oriented. Films can also be embossed, produced and / or processed according to other known film-forming processes. The films can be configured to specific applications by adjusting the thickness, materials and order of the various layers, as well as the additives applied or introduced in each layer.
    [034] The polymeric mixture comprising the first polyethylene and the second polyethylene can be formed into monolayer and / or multiple layer films using casting techniques, such as a cooling roll casting process. For example, a polymeric blend composition can be extruded in a molten state through a flat die and then cooled to form a film. As a specific example, cast films can be prepared using a cast film production machine as follows. Polymer pellets are melted at a temperature typically ranging from about 275 ° C to about 325 ° C for polymer casting (depending on the particular polymer (s) used, with the melting temperature being chosen to match the melting viscosity of the particular polymer (s). In the case of a multilayer cast film, the two or more different castings can be transported to a coextrusion adapter that combines the two or more melt streams into a coextruded multilayer structure. This layered flow can be distributed through a single extrusion film extrusion die to the desired width. The span opening of the die is typically about 600 pm (0.025 inch). The material can then be extracted in the final gauge. The material extraction ratio is typically about 21: 1 for 20 pm (0.8 millimeter) films. A vacuum box, flange pins, air knife or any combination thereof can be used to attach the melt that exits the die opening to a primary cooling roller maintained at about 32 ° C (80 ° F). The resulting film can be collected on a winder. The thickness of the film can be monitored by a gauge monitor and the film can be trimmed by a trimmer. A typical casting line rate is around 76.2 m to about 610 m (250 feet to about 2,000 feet) per minute. Those skilled in the field will appreciate that higher rates can be used for similar processes, such as extrusion coating. One or more optional treatments can be used to treat the film surface, if desired. Such cooling roller casting processes and apparatus can be as discussed and described, for example, in The Wiley-Encyclopedia of Packaging Technology, Second Edition, AL Brody and KS Marsh, Ed., John Wiley and Sons, Inc., New York (1997). Although cooling roll casting is an example, other forms of casting can be employed.
    [035] The polymeric mixture comprising the first polyethylene and the second polyethylene can be formed in monolayer and / or multiple layer films using blowing techniques, that is, to form a blown film. For example, the polymeric mixture can be extruded in a molten state through an annular matrix and then blown and cooled to form a blown tubular film which can then be axially cut and unfolded to form a flat film. As a specific example, blown films can be prepared as follows. The polymeric mixture can be introduced into the feed chute of an extruder, such as a 63.5 mm Egan extruder that is water cooled, heated by resistance and has a 24: 1 L / D ratio. The film can be produced using a 15.24 cm Sano matrix with a 2.24 mm matrix span, together with a non-adjustable, non-rotating Sano double-hole air ring. The film can be extruded through the die into a cooled film by blowing air over the film surface. The film can be extracted from the matrix, typically forming a cylindrical film that can be cooled, retracted and, optionally, subjected to a desired auxiliary process, such as cutting, treatment, sealing or printing. Typical melting temperatures can range from about 175 ° C to about 225 ° C. Film blowing rates can generally range from about 4.35 kg / hour / cm to about 26 kg / hour / cm (5 pounds / hour / inch to about 30 pounds / hour / inch) in circumference of the matrix. The finished film can be rolled up for further processing or fed to a bag making machine and converted into bags. A particular film blowing process and apparatus suitable for forming films can be as discussed and described, for example, in U.S. Patent No. 5,569,693. Of course, other methods of blowing film formation can also be used.
    [036] Films formed from a polymeric mixture comprising the first polyethylene and the second polyethylene can be uniaxially or biaxially oriented. Orientation in the direction of extrusion is known as orientation in the direction of the machine (Machine Direction - MD). Orientation perpendicular to the direction of extrusion is known as orientation in the transverse direction (Transverse Direction - TD). Orientation can be achieved by stretching or extracting a film first in the MD orientation, followed by TD. Blown films or cast films can also be oriented on the web following the film extrusion process, again in one or both directions. Orientation can be sequential or simultaneous, depending on the desired characteristics of the film. Preferred proportions of orientation can be about three to about six times the width extruded in the machine direction and between about four to about ten times the width extruded in the transverse direction. Typical commercial guidance processes are BOPP Tenter process, blown film and LISIM technology.
    [037] The total thickness of the resulting monolayer and / or multiple layers films may vary based, at least in part, on the particular end-use application. A total film thickness of about 5 pm to about 100 pm, more typically about 10 pm to about 50 pm, may be suitable for most applications. Those skilled in the field will appreciate that the thickness of individual layers for multi-layer films can be adjusted based on the desired end-use performance, polymer or copolymer employed, equipment capacity and other factors.
    [038] To facilitate the discussion of different film structures, the following notations are used here. Each layer of a film is denoted "A" or "B", where "A" indicates a film layer not containing the polymer mixture comprising the first polyethylene and the second polyethylene and "B" indicates a film layer having the mixture polymeric comprising the first polyethylene and the second polyethylene. The "B" layer may include the polymeric mixture comprising the first and second polyethylene or another mixture comprising the polymeric mixture and one or more other polymers. Where a film includes more than one layer A or more than one layer B, one or more symbols (',' ',' '', etc.) are attached to the symbol A or B to indicate layers of the same type which may be the same or may differ in one or more properties, such as chemical composition, density, melt index, thickness, etc. Finally, symbols for adjacent layers are separated by a slash (/). Using this notation, a three-layer film having an inner or central layer of a polymeric mixture comprising the first and second polyethylenes disposed between two layers of conventional outer film, that is, not containing a polymeric mixture comprising the first and second polyethylenes, would be denoted A / B / A '. Similarly, a film with five layers of alternating conventional / mixed polymer layers would be denoted A / B / A '/ B' / A ''. Unless otherwise indicated, the order of layers from left to right or from right to left does not matter, nor does the order of symbols matter. For example, an A / B film is equivalent to a B / A film and an A / A '/ B / A' 'film is equivalent to an A / B / A' / A '' film, for the purposes described here .
    [039] The relative thickness of each film layer is similarly denoted, with the thickness of each layer with respect to a total film thickness of 100 (without dimension) indicated numerically and separated by bars; for example, the relative thickness of an A / B / A 'film having layers A and A' of 10 pm each and a layer B of 30 pm is denoted as 20/60/20. Exemplary conventional films can be as discussed and described, for example, in U.S. Patent Nos. 6,423,420; 6,255,426; 6,265,055; 6,093,480; 6,083,611; 5,922,441; 5,907,943; 5,907,942; 5,902,684; 5,814,399; 5,752,362; 5,749,202; 7,235,607; 7,601,409; RE 38,658; RE 38,429; U.S. Patent Publication 2007/0260016; and WO Publication No. WO2005 / 065945.
    [040] For the various films described here, the "A" layer can be formed from any material known in the art for use in multilayer films or in film coated products. Thus, for example, layer A can be formed of a polyethylene (homopolymer or copolymer) and the polyethylene can be, for example, a VLDPE, LDPE, LLDPE, MDPE, HDPE, as well as other polyethylene known in the art. In another example, layer A may be formed of a polyethylene (homopolymer or copolymer), a non-polyethylene polymer, for example, a polypropylene or a mixture of polyethylene and a non-polyethylene polymer.
    [041] Additional illustrative polymers (non-polyethylenes) that can be used as or in layer A may include, but are not limited to, other polyolefins, polyamides, polyesters, polycarbonates, polysulfones, polyacetals, polylactones, acrylonitrile-butadiene-styrene resins , polyphenylene oxide, polyphenylene sulfide, styrene acrylonitrile resins, maleic styrene anhydride, polyimides, aromatic polyketones or mixtures of two or more of the above. Suitable polyolefins may include, but are not limited to, polymers comprising one or more C2 to C40 linear, branched or cyclic olefins, preferably polymers comprising copolymerized propylene with one or more C3 to C40 olefins, preferably a C3 to C20 alpha olefin, more preferably C3 to C10 alpha-olefins.
    [042] In structures with multiple layers, one or more layers A can also be a bonding layer that promotes adhesion, such as PRIMACOR® ethylene-acrylic acid copolymers available from Dow Chemical Co. and / or ethylene-acetate copolymers vinyl. Other materials for layers A may be, for example, sheet, nylon, ethylene-vinyl alcohol copolymers, polyvinylidene chloride, polyethylene terephthalate, oriented polypropylene, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, copolymers of ethylene-methacrylic acid, grafted and paper-modified polymers.
    [043] One or more layers A can be replaced by a layer of substrate, such as glass, plastic, paper, metal, etc. or the entire film can be coated or laminated on a substrate. Thus, although the discussion here has focused on films with multiple layers, films having a mixture comprising the first polyethylene and the second polyethylene can also be used as coatings; for example, films (monolayer and multiple layers) can be coated on a substrate, such as paper, metal, glass, plastic and other materials capable of accepting a coating.
    [044] The "B" layer can be formed from a polymeric mixture comprising the first polymer and the second polymer and can be any of such mixtures described here. In one example, layer B can be formed from a polymeric mixture comprising from about 0.1% by weight to about 99.9% by weight of the first polyethylene and from about 99.9% by weight to about 0 , 1% by weight of the second polyethylene. The "A" layer can be formed from a polymer or a mixture of one or more polymers which can include very low density polyethylene, medium density polyethylene, differentiated polyethylene or any combination thereof. In a multilayer film, layer "A" can be formed from the first polyethylene and layer "B" can be formed from a polymeric mixture comprising the first polyethylene and the second polyethylene.
    [045] The polymeric film can be a multilayered film with any of the following exemplary structures: (a) films with two layers, such as A / B and B / B '; (b) films with three layers, such as A / B / A ', A / A' / B, B / A / B 'and B / B' / B ''; (c) films with four layers, such as A / A '/ A' '/ B, A / A' / B / A '', A / A '/ B / B', A / B / A '/ B ', A / B / B' / A ', B / A / A' / B ', A / B / B' / B '', B / A / B '/ B' 'and B / B' / B ''/B'''; (d) films with five layers, such as A / A '/ A' '/ A' '' / B, A / A '/ A' '/ B / A' '', A / A '/ B / A '' / A '' ', A / A' / A '' / B / B ', A / A' / B / A '' / B ', A / A' / B / B '/ A' ', A / B / A '/ B' / A '', A / B / A '/ A' '/ B, B / A / A' / A '' / B ', A / A' / B / B ' / B '', A / B / A '/ B' / B '', A / B / B '/ B' '/ A', B / A / A '/ B' / B '', B / A / B '/ A' / B '', B / A / B '/ B' '/ A', A / B / B '/ B' '/ B' '', B / A / B '/ B' '/ B' '', B / B '/ A / B' '/ B' '' and B / B '/ B' '/ B' '' / B '' ''; and similar structures for films having six, seven, eight, nine, twenty-four, forty-eight, sixty-four, a hundred or any other number of layers. It will be appreciated that films having even more layers can be formed using polymeric mixtures and such films are within the scope of the invention.
    [046] Any of the polymers discussed and described here, for example, the first polyethylene, second polyethylene, VLDPEs, LDPEs, LLDPEs, MDPEs, HDPEs and the like, can be prepared via any known process or combination of processes including, but not limited to a, processes in solution, paste, high pressure and / or gas phase. Gas phase polymerization processes suitable for the production of the first polyethylene and / or the second polyethylene are described in U.S. Patent Nos. 3,709,853; 4,003,712; 4,011,382; 4,302,566; 4,543,399; 4,588,790; 4,882,400; 5,028,670; 5,352,749; 5,405,922; 5,541,270; 5,627,242; 5,665,818; 5,677,375; 6,255,426; European Patents Nos. EP0802202; EP0794200; EP0649992 EP0634421; and Belgian Patent No. 839,380. Examples of solution or paste polymerization processes are described in U.S. Patent Nos. 4,271,060; 4,613,484; 5,001,205; 5,236,998; and 5,589,555.
    [047] Any catalyst or combination of catalysts suitable for the production of polyethylene and other polymers can be used in any one or more polymerization processes to produce the first polyethylene, the second polyethylene, the polymer mixture and / or other polymers that can be used in conjunction with the polymeric mixture. Illustrative catalysts may include, but are not limited to, Ziegler-Natta catalysts, chromium-based catalysts, metallocene catalysts and other single-site catalysts, including catalysts containing Group 15, bimetallic catalysts and mixed catalysts. The catalyst or catalyst system can also include AlCl3, cobalt, iron, palladium, chromium / chromium oxide or "Phillips" catalysts. Any catalyst can be used alone or in combination with any other catalyst.
    [048] Metallocenes are, in general, fully described, for example, in 1 & 2 Metallocene-Based Polyolefins (John Scheirs & W. Kaminsky, eds., John Wiley & Sons, Ltda. 2000); G.G. Hlatky in 181 Coordination Chem. Rev. 243-296 (1999) and, in particular, for use in the synthesis of polyethylene, in 1 Metallocene-Based Polyolefins 261-377 (2000). Other suitable metallocene catalyst compounds can include, but are not limited to, metallocenes described in U.S. Patent Nos. 7,179,876; 7,169,864; 7,157,531; 7,129,302; 6,995,109; 6,958,306; 6.884748; 6,689,847; 5,026,798; 5,703,187; 5,747,406; 6,069,213; 7,244,795; 7,579,415; U.S. Patent Application Publication No. 2007/0055028; and WO WO 97/22635 publications; WO 00/699/22; WO 01/30860; WO 01/30861; WO 02/46246; WO 02/50088; WO 04/022230; WO 04/026921; and WO 06/019494.
    [049] The "Group 15 containing catalyst" may include metal complexes from Group 3 to Group 12, where the metal has 2 to 8 coordinates, the coordinating portion or portions including at least two Group 15 atoms and up to four atoms Group 15. For example, the Group 15 containing catalyst component can be a complex of a Group 4 metal and one to four linkers, so that the Group 4 metal has at least 2 coordinates, the coordinating portion or portions including at least two nitrogens. Representative Group 15 containing compounds are described in WO Publication No. WO 99/01460; European Publications Nos. EP0893454A1; EP 0894005A1; U.S. Patent Nos. 5,318,935; 5,889,128; 6,333,389; and 6,271,325.
    [050] Illustrative Ziegler-Natta catalyst compounds are described in Ziegler Catalysts 363-386 (G. Fink, R. Mulhaupt and H.H. Brintzinger, eds. Springer-Verlag 1995); European Patents Nos. EP 0103120; EP 1102503; EP 0231102; EP 0703246; U.S. Patent Nos. RE 33,683; 4,115,639; 4,077,904; 4,302,565; 4,302,566; 4,482,687; 4,564,605; 4,721,763; 4,879,359; 4,960,741; 5,518,973; 5,525,678; 5,288,933; 5,290,745; 5,093,415; and 6,562,905; and U.S. Patent Application Publication No. 2008/0194780. Examples of such catalysts include those comprising Group 4, 5 or 6 transition metal oxide, alkoxide and halide compounds or titanium, zirconium or vanadium oxide, alkoxide and halide compound; optionally in combination with a magnesium compound, internal and / or external electron donors (alcohols, ethers, siloxanes, etc.), alkyl and alkyl boron or aluminum halides and inorganic oxide supports.
    [051] Suitable chromium catalysts can include disubstituted chromates, such as CrO2 (OR) 2; where R is triphenyl silane or a tertiary polyalicyclic alkyl. The chromium catalyst system can further include CrO3, chromocene, silyl chromate, chromyl chloride (CrO2Cl2), chromium 2-ethylhexanoate, chromium acetylacetonate (Cr (AcAc) 3) and the like. Other non-limiting examples of chromium catalysts can be as discussed and described in U.S. Patent No. 6,989,344.
    [052] The mixed catalyst can be a bimetallic catalyst composition or a multiple catalyst composition. As used herein, the terms "bimetallic catalyst composition" and "bimetallic catalyst" include any composition, mixture or system that includes two or more different catalyst components, each having a different metal group. The terms "composition with multiple catalysts" and "multiple catalysts" include any composition, mixture or system that includes two or more different catalyst components, regardless of the metals. Therefore, the terms "bimetallic catalyst composition", "bimetallic catalyst", "composition with multiple catalysts" and "multiple catalysts" will be collectively referred to herein as a "mixed catalyst", unless otherwise specifically mentioned. In one example, the mixed catalyst includes at least one metallocene catalyst component and at least one non-metallocene component.
    [053] In some embodiments, an activator can be used with the catalyst compound. As used herein, the term "activator" refers to any compound or combination of compounds, supported or unsupported, which can activate a catalyst component or component, such as by creating a cationic species of the catalyst component. Illustrative activators include, but are not limited to, aluminoxane (for example, methylaluminoxane "MAO"), modified aluminoxane (for example, modified methylaluminoxane "MMAO" and / or tetraisobutyl dialuminoxane "TIBAO") and alkyl aluminum compounds, ionization activators (neutral or ionic), such as tetrakis (pentafluorophenyl) tri (n-butyl) ammonium boron, can also be used and combinations thereof.
    [054] The catalyst compositions can include a carrier material or vehicle. As used herein, the terms "support" and "vehicle" are used interchangeably and are any support material, including a porous support material, for example, talc, inorganic oxides and inorganic chlorides. The component (s) of the catalyst and / or activator (s) can be deposited on, contacted with, vaporized with, attached to or incorporated into, adsorbed or absorbed on or on one or more supports or vehicles. Other support materials may include resinous support materials, such as polystyrene, functionalized or cross-linked organic supports, such as polymeric compounds or polyolefins of divinyl benzene polystyrene, zeolites, clays or any other organic or inorganic support material and mixtures thereof. . Suitable catalyst supports can be as discussed and described, for example, in Hlatky, Chem. Rev. (2000), 100, 1347 1376 and Fink et al., Chem. Rev. (2000), 100, 1377-1390, U.S. Patent Nos .: 4,701,432. 4,808,561; 4,912,075; 4,925,821; 4,937,217; 5,008,228; 5,238,892; 5,240,894; 5,332,706; 5,346,925; 5,422,325; 5,466,649; 5,466,766; 5,468,702; 5,529,965; 5,554,704; 5,629,253; 5,639,835; 5,625,015; 5,643,847; 5,665,665; 5,698,487; 5,714,424; 5,723,400; 5,723,402; 5,731,261; 5,759,940; 5,767,032; 5,770,664; and 5,972,510; and PCT Publications Nos. WO 95/32995; WO 95/14044; WO 96/06187; WO 97/02297; WO 99/47598; WO 99/48605; and WO 99/50311.
    Film Properties [055] Stretch films in monolayer and multiple layers that include the polymer mixture comprising the first polyethylene and the second polyethylene may be free of tiger stripe formation when stretched. For example, stretch films that include the polymer blend comprising the first polyethylene and the second polyethylene may be exempt from tiger streak formation from 0% stretch to more than 50% stretch, more than 100% stretch, more than 150% stretch, more than 200% stretch, more than 225% stretch, more than 250% stretch or more than 275% stretch. In other words, a stretch film that includes the polymer blend can be stretched from an initial state or "as produced" until the film breaks without showing a tiger streak.
    [056] Stretch films can be monolayer or multiple layers, with one or more layers comprising the polymeric mixture. Stretch films may be coextruded and may include a layer comprising the polymeric mixture discussed and described here, together with one or more layers of metallocene catalyst LLDPE or traditional Ziegler-Natta, which may optionally include a comonomer, such as 1-hexene , 1-butene and / or 1-octene, for example.
    [057] Stretch films can have a final Highlight Stretch greater than or equal to about 220%, about 230%, about 240%, about 250%, about 260%, about 270%, about 280 %, about 290% or about 300%. Adherent stretch films may have a Highlight final stretch force greater than or equal to about 267 N (60 pounds), about 311 N (70 pounds), about 334 N (75 pounds), about 356 N (80 pounds), about 378 N (85 pounds), or about 400 N (90 pounds).
    [058] Highlight final stretch, reported as a percentage, and the final Highlight stretch force, reported in Newtons (N) and pounds strength (pounds), were measured by a Highlight Stretch tester using the recommended settings for the Highlight machine and normal practices in the industry. The occurrence of tiger streak formation was visually observed and recorded during the final stretch test. Results are reported as an average of three tests, unless otherwise noted. The nominal pre-stretch thickness for all films discussed here was 20.3 pm (0.80 mm).
    [059] Adhesive stretch films can have an initial or first 0% (parallel) adhesion value of about 52.5 Newtons / meter (140 grams-force per inch width), about 57.8 Newtons / meter (150 grams-force per inch), about 61.3 Newtons / meter (160 grams-force per inch), about 64.8 Newtons / meter (170 grams-force per inch), about 68.3 Newtons / meter (180 grams-force per inch), about 71.8 Newtons / meter (190 grams-force per inch), about 77 Newtons / meter (200 grams-force per width) inch), about 80.5 Newtons / meter (210 grams-force per inch in inches), about 84 Newtons / meter (220 grams-force per inch in inches), about 87.5 Newtons / meter (230 grams-force per inch width), about 91 Newtons / meter (240 grams-force per inch inch) or about 96.3 Newtons / meter (250 grams-force per inch width). Adherence to adherent stretch films can be measured according to the standard ASTM D 5458 test according to the following procedure. For the ASTM D 5448 test, the test speed is set at 2.1 x 10-3 meters / sec (5 inches / min) and only the upper test strip is stretched to the desired percentage stretch. The modified test used for the values provided here uses a test speed of 1.6 x 10-3 meters / sec (3.94 inches / min) and the upper test strip and the lower test strip (platform) are stretched until the desired percentage stretch.
    [060] Adhesive stretch films that include the polymeric mixture comprising the first polyethylene and the second polyethylene can be described as having an initial adhesion value or a first value at 0% stretch and a second adhesion value at 200% stretch. The second adhesion value at 200% stretch can be greater than about 45% of the first adhesion value. In another example, the second adhesion value at 200% stretch can range from about 40% to about 60% of the first adhesion value, about 40% to about 55% of the first adhesion value, about 44 % to about 53% of the first adhesion value or about 42% to about 58% of the first adhesion value. In another example, the second 200% stretch adhesion value can be greater than about 44%, about 45%, 46%, about 47%, about 48%, about 49%, about 50 %, about 51% or about 52% of the first adhesion value. For example, a sticky stretch film having a first adhesion value at 0% stretch of 57.8 Newtons / meter (150 grams-force per inch width) may have a second adhesion value at 200% stretch greater than about 26.2 Newtons / meter (67.5 grams-force per inch width).
    [061] The polymeric mixture discussed and described here may also be suitable for use in manually wound stretch films. Manually wound stretch films require a combination of excellent toughness, especially perforation, MD tearing performance, free-fall performance and rigidity, ie, difficulty in stretching, the film. The stiffness of the film minimizes the stretching required to provide adequate load-bearing force for a rolled load and to prevent further stretching of the film. Film toughness may be required because loads on manually wound film (which are being wound up) are typically more irregular and often contain higher drilling requirements than stretch loads on typical machines. Manually wound stretch films can exhibit a Highlight final stretch force greater than or equal to about 267 N (60 pounds), about 311 N (70 pounds), about 334 N (75 pounds), about 356 N ( 80 pounds), about 378 N (85 pounds), about 400 N (90 pounds), about 445 N (100 pounds) or about 556 N (125 pounds).
    Examples [062] To provide a better understanding of the preceding discussion, the following non-limiting examples are provided. Although the examples are directed to specific modalities, they should not be seen as limiting the invention in any respect. All parts, proportions and percentages are by weight, unless otherwise indicated.
    [063] A first polyethylene (1 ° PE) was used to prepare a comparative exemplary multilayer film (CEx1). Two films with multiple additional layers (Ex. 1 and Ex. 2) were also prepared and included at least one layer formed from a polymeric mixture comprising the first polyethylene and a second polyethylene (2 ° PE). Table 1 lists some properties for the first polyethylene (1 ° PE) and the second polyethylene (2 ° PE).
    [064] Cast films were extruded on a 0.08 meter (3.5 ") Black Clawson line (30: 1 L: D) equipped with a 1.06 meter (42") slot matrix. The line speed was set at 750 feet / min and the total productivity was adjusted (typically 4x10 to 4.16 x 10 meters / second (575-590 pounds / h)) to obtain a film having a nominal thickness of 0.8 mm. A standard "elevation" temperature profile was used, where "BZ" is a barrel zone: BZ1 = 176.7 ° C (350 ° F), BZ2 = 232.2 ° C (450 ° F), BZ3 = 273 , 9 ° C (525 ° F), BZ4 = 282.2 ° C (540 ° F), BZ5 = 276.7 ° C (530 ° F), BZ6 = 276.7 ° C (530 ° F) and Matrix = 287.8 ° C (550 ° F). The edge of the film was trimmed to provide a 0.50 meter (20 ") roll for testing. The three multilayer films, ie CEx. 1, Ex. 1 and Ex. 2, had the A / A '/ structures A, A / B / A and B '/ B / B', respectively. Each film has a thickness ratio of 10/80/10 and an overall thickness of 20.3 pm (0.80 mm). the three films (CEx. 1, Ex. 1 and Ex. 2) are shown in Table 2.
    [065] The CEx film. 1 was formed only from the first polyethylene (1 ° PE) and had a 70% stretch tiger streak beginning which ended in about 183% stretch. Surprisingly and unexpectedly, tiger streak formation was not seen in Ex. 1 and Ex. 2, in which the polymer mixture containing the first polyethylene (1 ° PE) and the second polyethylene (2 ° PE) was used in at least a layer. The Ex. 1 film used the polymeric mixture only in the inner or central layer, while the Ex. 2 film used the polymeric mixture in all three layers.
    [066] Additionally, Ex. 1 and Ex. 2 exhibited, surprisingly and unexpectedly, increased adhesion after stretching to 200%, when compared to CEx. 1. More particularly, the comparative example CEx. 1 had an initial (parallel) zero-stretch (0%) adhesion of 54.3 Newtons / meter (145 grams-force per inch) and only 24.5 Newtons / meter (63 grams-force per inch) at 200% stretch, a loss of 31.5 Newtons / meter (82 grams-force per inch width). Ex. 1, however, had an initial (parallel) zero-stretch (0%) adhesion of 54.3 Newtons / meter (144 grams-force per inch width) and 28.9 Newtons / meter (75 grams-force per inch width) at 200% stretch, a loss of just 26.2 Newtons / meter (69 grams-force per inch width). Example 2 had a zero stretch (parallel) adhesion (0%) of 73.5 Newtons / meter (194 grams-force per inch width), which was 19.2 Newtons / meter (49 grams-force per width inch) larger than CEx. 1. In addition, Ex. 2 had a 200% (parallel) 200% stretch (parallel) grip (92 grams-force per inch width), which is about 10.5 Newtons / meter (29 grams- force per inch in width) greater than CEx. 1. Ex. 1 and Ex. 2 had adherence values at 200% stretch which were greater than 45% of the initial adherence values of the film at zero stretch (0%), while CEx. 1 had an adherence value at 200% stretch which was less than 45% of the initial adhesion value of the film at zero stretch (0%).
    [067] The Comparative Example CEx. 2 and examples Ex. 3, Ex. 4, Ex. 5 and Ex. 6 were also prepared as films with three layers having the structure A / A '/ A, with all three layers having the same composition as the others. The films all had a thickness ratio of 10/80/10 and an overall thickness of 20.3 pm (0.80 mm). For CEx. 2, the polyethylene used was an LLDPE ethylene / hexane copolymer from Ziegler Natta. For Ex. 3, the polyethylene used was an LLDPE ethylene / hexane copolymer from Ziegler Natta. For Ex. 4, the polyethylene used was an LLDPE ethylene / octene copolymer by Ziegler Natta. For Ex. 5, the polyethylene used was an LLDPE copolymer of ethylene / metallocene hexane. For Ex. 6, the polyethylene used was a 70/30 polymer blend of the polyethylene used in Ex. 5 and another LLDPE ethylene / metallocene hexane copolymer. Table 3 shows some properties for the polyethylene used in CEx. 2 and Ex. 3-6.
    [068] Properties for the five films (CEx. 2 and Ex. 36) are shown in Table 4. The films were prepared on a Black Clawson line, similar to CEx. 1, Ex. 1 and Ex. 2, discussed above.
    [069] Ex. 3 is a polyethylene made from the same catalyst and under conditions similar to CEx polyethylene. 2. The polymerization conditions were modified, so that the melting index (I2) for Ex. 3 was reduced from 3.31 g / 10 min to 2.23 g / 10 min. Reduction of the melting index (I2) eliminated, surprisingly and unexpectedly, the formation of tiger stripes in Ex. 3. Without wishing to be bound by theory, it is believed that reduction of the melting index (I2) of the comparative example CEx. 2 eliminates the formation of tiger stripes due to the promotion of hardening, which minimizes the tendency of localized deformation.
    Consequently, modification of the polymerization conditions of a particular polyethylene, so that the melt index is reduced, can produce a polyethylene suitable for use in stretch films or adherent stretch films that do not exhibit any tiger streak formation during stretching.
    [070] Ex. 4 was prepared from a polyethylene produced using a Ziegler-Natta catalyst different from the polyethylenes in CEx. 1, CEx. 2 and Ex. 3. The melting index (I2) for Ex. 4 was 2.35 g / 10 min. Some desirable properties for polyethylenes used to produce stretch films that do not exhibit tiger streak formation can be derived from the data provided from CEx. 1, CEx. 2 and Ex. 3 and Ex. 4. For a single LLDPE, that is, not a mixture of two or more polyethylenes, a desirable property appears to be that a melt index of less than about 2.45 may tend to produce films that do not exhibit tiger streak formation when stretched. Polyethylenes in CEx. 1 and CEx. 2 have a melt index greater than 2.45 and the polyethylenes in Ex. 3 and Ex. 4 have a melt index of less than 2.45. As such, instead of preparing films from a polymeric mixture comprising the first polyethylene and the second polyethylene, as discussed and described here, it is possible to modify the polymerization conditions for a single polyethylene, that is, not a mixture of two or more polyethylenes, so that the melt index is reduced. As shown in Ex. 3 and Ex. 4, films prepared from polyethylene having a reduced melt index may be exempt from tiger streak formation when stretched.
    [071] It is also noteworthy that Ex. 5 and Ex. 6, contrary to the prior art, exhibited a higher initial adhesion than Ex. 4, although having a lower amount of hexane extractables. The expected trend in adherence is that adherence decreases as the amount of hexane extractables is decreased. In direct contrast to the prior art, however, the initial adherence to Ex. 5 and Ex. 6 was greater than Ex. 4, which had a significantly higher content of hexane extractables (43.1 and 40.9 Newtons / meter (112 and 106 grams-force per inch width), respectively, when compared to 35.1 Newtons / meter (91 grams-force per inch width). Without wishing to be bound by theory, it is believed that the Ex 5 and Ex. 6 had a much smoother film surface than Ex. 4, as suggested by AFM (Atomic Force Microscopy) photographs. The smooth film surface of Ex. 5 and Ex. 6 it was due to the unique morphology of that particular product family.
    [072] The Short Chain Branching (SCB) branch can be determined by means of 1HRMN (proton nuclear magnetic resonance) with data collected at 500 MHz. The spectra can be taken as a reference by configuring the signal of the main polymeric part to 1,347 ppm. The methyl group contents in ethylene / 1-olefin copolymers can be calculated from the 1HRMN spectrum using the following formula: Methyl groups / 1000 carbons = (ICH3 * 0, 33 * 1000) (I0,5-2,1PPm * 0.5), where Ich3 is the methyl signal area normalized in the region between 0.88 and 1.05 ppm and Io, 5-2, ippm is the area between 0.50 and 2.10 ppm. The number of methyl groups corresponds to the number of short chain branches in polyethylene assuming that the short chain branches contain 1 methyl group (-CH3) and that all methyl groups are a result of short chain branching.
    [073] The 1% secant module (MD and TD) was determined according to ASTM D882-97. The caliber of the film was measured according to ASTM D5947-96, Method C, except that the micrometer calibration was performed annually with a commercially available calibration block (Starret Webber 9, JCV1 & 2).
    [074] Tensile strength values (elasticity limit, tensile strength, elongation limit and elongation at break) were measured in the machine direction (Machine Direction - "MD") and transverse direction (Transverse Direction - "TD") ) according to ASTM D882-97. The film caliber was measured using ASTM D5947-96, Method C, except that the micrometer calibration was performed annually with a commercially available calibration block (Starret Webber 9, JCV1 & 2).
    [075] The tearing of Elmendorf was determined according to ASTM D1922-94a. The film caliber was measured according to ASTM D374-94, Method C, except that the micrometer calibration was performed annually with a commercially available calibration block (Starret Webber 9, JCV1 & 2).
    [076] Resistance to impact in free fall, reported in grams per micrometer (g / pm), was measured as specified by ASTM D-1709, method A.
    [077] Turbidity (%) was determined according to ASTM D1003-97 using the alternative Haze Shortcut Procedure.
    [078] The Highlight drilling force, reported in pounds (lb), was measured by a Highlight stretch tester using a method consistent with the recommended settings for the Highlight machine. Results are reported as an average of two tests, unless otherwise noted.
    [079] Caliber: the thickness of the film was measured according to ASTM D374-94, Method C, except that the micrometer calibration was performed annually with a commercially available calibration block (Starret Webber 9, JCV1 & 2).
    [080] Density has been measured according to ASTM D-792.
    [081] MI (I2) was measured according to ASTM D-1238-E (at 190 ° C, weight of 2.16 kg).
    [082] FI (I21) was measured according to ASTM D-1238-F (at 190 ° C, weight 21.6 kg).
    [083] Mw, Mn and Mz were measured using gel permeation chromatography (Gel Permeation Chromatography - GPC), also known as size exclusion chromatography (Size Exclusion Chromatography - SEC), as described above.
    权利要求:
    Claims (13)
    [1]
    1. Polymeric mixture, characterized by the fact that it comprises: a linear low density polyethylene (LLDPE) having a density ranging from 0.910 g / cm3 to 0.930 g / cm3, a melting index (I2) greater than 1 g / 10 min and less than 20 g / 10 min, and a melt index ratio (I21 / I2) less than 30; and a low density polyethylene (LDPE) having a density less than 0.940 g / cm3, a melt index (I2) of 0.01 to 0.8 g / 10min, a ratio of melt index (I21 / I2 ) greater than 30 and a molecular weight distribution (Mw / Mn) less than 4.5, Mw and Mn being determined using gel permeation chromatography, the density being determined according to ASTM D-792, I2 being determined using ASTM D-1238E (at 190 ° C, using a weight of 2.16 kg) and I21 being determined using ASTM D-1238F (at 190 ° C using a weight of 21.6 kg).
    [2]
    2. Polymeric mixture according to claim 1, characterized by the fact that the proportion of melting index (I21 / I2) of low density polyethylene (LDPE) ranges from 33 to 150 and the molecular weight distribution (Mw / Mn ) of low density polyethylene (LDPE) ranges from 3 to 4.2.
    [3]
    Polymeric mixture according to either of claims 1 or 2, characterized in that the low density polyethylene (LDPE) is present in an amount of 5% by weight to 40% by weight based on the combined total weight of the linear low density polyethylene (LLDPE) and low density polyethylene (LDPE).
    [4]
    Polymeric mixture according to any one of claims 1 to 3, characterized in that the linear low density polyethylene (LLDPE) comprises a copolymer derived from ethylene and one or more comonomers from C3 to C20 α-olefin and being that low density polyethylene (LDPE) comprises a copolymer derived from ethylene and one or more comonomers from C3 to C20 α-olefin.
    [5]
    Polymeric mixture according to any one of claims 1 to 4, characterized in that the density of linear low density polyethylene (LLDPE) ranges from 0.915 g / cm3 to 0.925 g / cm3 and the density of the polyethylene of low density (LDPE) ranges from 0.915 g / cm3 to 0. 925 g / cm3.
    [6]
    Polymeric mixture according to any one of claims 1 to 5, characterized by the fact that linear low density polyethylene (LLDPE) has a molecular weight distribution (Mw / Mn) of 4.1 to 5.5, and with low density polyethylene (LDPE) having a molecular weight distribution (Mw / Mn) of 3 to 4.
    [7]
    7. Film, characterized by the fact that it comprises the mixture as defined in any one of claims 1 to 6.
    [8]
    8. Film according to claim 7, characterized by the fact that linear low density polyethylene (LLDPE) has a density in the range of 0.915 g / cm3 to 0.940 g / cm3, a higher melting index (I2) than 1 g / 10 min and less than 20 g / 10 min and a melt index ratio (I21 / I2) between 20 and less than 30.
    [9]
    Film according to either of claims 7 or 8, characterized by the fact that low density polyethylene (LDPE) has a density in the range of 0.915 g / cm3 to 0.930 g / cm3, a melting index ( I2) in the range of 0.01 g / 10 min to 0.8 g / 10 min and a fusion index ratio (I21 / I2) greater than 30 and up to 150 and a molecular weight distribution (Mw / Mn) in range from 3 to 4.5.
    [10]
    10. Film according to either of claims 8 or 9, characterized in that the film is an adherent stretch film, and the film comprises an adhesive.
    [11]
    11. Film according to claim 10, characterized in that the adherent stretch film has a first 0% stretch adhesion value of 5.51 grams-force per millimeter in width (70 grams-force per inch in width) or more and a second adhesion value of 2.70 grams-force per millimeter in width (70 grams-force per inch in width) or more after stretching to 200%, the adhesion value being measured according to the ASTM D5458 test, using a test speed of 3.94 inches / minute (100 mm / minutes) with both the upper test strip and the lower test strip (platform) being stretched to the desired percentage stretch.
    [12]
    12. Film according to claim 10, characterized by the fact that the adherent stretch film has a first adherence value at 0% stretch and the adherent stretch film has a second adherence value after stretching to 200% which is greater than than 45% of the first adhesion value, the adhesion values being measured according to the ASTM D5458 test, using a test speed of 3.94 inch / minute (100 mm / minute) with both the upper and lower test strips lower test strip (platform) being stretched to the desired percentage stretch.
    [13]
    13. Film according to claim 11, characterized by the fact that the adherent stretch film stretches at least 200%, without showing tiger streak formation, visually observed using a pre-stretched film of nominal thickness of 0.8 mil (20.3 microns).
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4003712A|1970-07-29|1977-01-18|Union Carbide Corporation|Fluidized bed reactor|
    US3709853A|1971-04-29|1973-01-09|Union Carbide Corp|Polymerization of ethylene using supported bis-chromiumcatalysts|
    US4115639A|1971-06-24|1978-09-19|Union Carbide Corporation|Ethylene polymerization with ether modified catalyst|
    US4011382A|1975-03-10|1977-03-08|Union Carbide Corporation|Preparation of low and medium density ethylene polymer in fluid bed reactor|
    US4077904A|1976-06-29|1978-03-07|Union Carbide Corporation|Olefin polymerization process and catalyst therefor|
    US4302566A|1978-03-31|1981-11-24|Union Carbide Corporation|Preparation of ethylene copolymers in fluid bed reactor|
    US4302565A|1978-03-31|1981-11-24|Union Carbide Corporation|Impregnated polymerization catalyst, process for preparing, and use for ethylene copolymerization|
    US4271060A|1979-09-17|1981-06-02|Phillips Petroleum Company|Solution polymerization process|
    US4482687A|1979-10-26|1984-11-13|Union Carbide Corporation|Preparation of low-density ethylene copolymers in fluid bed reactor|
    US4588790A|1982-03-24|1986-05-13|Union Carbide Corporation|Method for fluidized bed polymerization|
    US4543399A|1982-03-24|1985-09-24|Union Carbide Corporation|Fluidized bed reaction systems|
    EP0099774B2|1982-06-24|1995-03-22|BP Chimie Société Anonyme|Process for the polymerization and copolymerization of alpha-olefins in a fluidized bed|
    JPS5920308A|1982-07-26|1984-02-02|Toyo Sutoufuaa Chem:Kk|Production of catalyst component for alpha-olefin polymerization|
    US4540753A|1983-06-15|1985-09-10|Exxon Research & Engineering Co.|Narrow MWD alpha-olefin copolymers|
    FR2555182B1|1983-11-23|1986-11-07|Bp Chimie Sa|PROCESS FOR THE PREPARATION OF A SUPPORTED CATALYST FOR THE COPOLYMERIZATION OF ETHYLENE WITH SUPERIOR ALPHA-OLEFINS|
    US4613484A|1984-11-30|1986-09-23|Phillips Petroleum Company|Loop reactor settling leg system for separation of solid polymers and liquid diluent|
    US4808561A|1985-06-21|1989-02-28|Exxon Chemical Patents Inc.|Supported polymerization catalyst|
    US4701432A|1985-11-15|1987-10-20|Exxon Chemical Patents Inc.|Supported polymerization catalyst|
    USRE33683E|1986-01-24|1991-09-03|Mobil Oil Corporation|Catalyst composition for polymerizing alpha-olefins|
    US4732882A|1986-01-24|1988-03-22|Mobil Oil Corporation|Catalyst composition for polymerizing alpha-olefins|
    FR2609036B1|1986-12-29|1989-04-14|Bp Chimie Sa|POLYMERIZATION OR COPOLYMERIZATION OF ETHYLENE IN THE GASEOUS PHASE IN THE PRESENCE OF A PREPOLYMER COMPRISING A CHROMIUM OXIDE CATALYST|
    US5093415A|1987-05-19|1992-03-03|Union Carbide Chemicals & Plastics Technology Corporation|Process for producing stereoregular polymers having a narrow molecular weight distribution|
    FR2618786B1|1987-07-31|1989-12-01|Bp Chimie Sa|PROCESS FOR THE POLYMERIZATION OF GASEOUS OLEFINS IN A FLUIDIZED BED REACTOR|
    US4912075A|1987-12-17|1990-03-27|Exxon Chemical Patents Inc.|Method for preparing a supported metallocene-alumoxane catalyst for gas phase polymerization|
    US4925821A|1987-12-17|1990-05-15|Exxon Chemical Patents Inc.|Method for utilizing triethyaluminum to prepare an alumoxane support for an active metallocene catalyst|
    US4937217A|1987-12-17|1990-06-26|Exxon Chemical Patents Inc.|Method for utilizing triethylaluminum to prepare an alumoxane support for an active metallocene catalyst|
    FR2628110B1|1988-03-03|1994-03-25|Bp Chimie|CATALYST FOR POLYMERIZATION OF ZIEGLER-NATTA-TYPE OLEFINS, SUPPORTED ON SPHERICAL MAGNESIUM CHLORIDE PARTICLES, AND PROCESS FOR PREPARING THE SAME|
    US5008228A|1988-03-29|1991-04-16|Exxon Chemical Patents Inc.|Method for preparing a silica gel supported metallocene-alumoxane catalyst|
    US5001205A|1988-06-16|1991-03-19|Exxon Chemical Patents Inc.|Process for production of a high molecular weight ethylene α-olefin elastomer with a metallocene alumoxane catalyst|
    FR2634212B1|1988-07-15|1991-04-19|Bp Chimie Sa|APPARATUS AND METHOD FOR POLYMERIZATION OF GASEOUS OLEFINS IN A FLUIDIZED BED REACTOR|
    NZ235032A|1989-08-31|1993-04-28|Dow Chemical Co|Constrained geometry complexes of titanium, zirconium or hafnium comprising a substituted cyclopentadiene ligand; use as olefin polymerisation catalyst component|
    US5026798A|1989-09-13|1991-06-25|Exxon Chemical Patents Inc.|Process for producing crystalline poly-α-olefins with a monocyclopentadienyl transition metal catalyst system|
    EP0569388B1|1990-12-27|1996-03-13|Exxon Chemical Patents Inc.|An amido transition metal compound and a catalyst system for the production of isotactic polypropylene|
    US5236998A|1991-03-07|1993-08-17|Occidental Chemical Corporation|Process for the manufacture of linear polyethylene containing α-alkene commonomers|
    US5466766A|1991-05-09|1995-11-14|Phillips Petroleum Company|Metallocenes and processes therefor and therewith|
    US5589555A|1991-10-03|1996-12-31|Novacor Chemicals S.A.|Control of a solution process for polymerization of ethylene|
    US5352749A|1992-03-19|1994-10-04|Exxon Chemical Patents, Inc.|Process for polymerizing monomers in fluidized beds|
    US5288933A|1992-04-16|1994-02-22|Union Carbide Chemicals & Plastics Technology Corporation|Process for the production of polyethylene|
    US5240894A|1992-05-18|1993-08-31|Exxon Chemical Patents Inc.|Method for making and using a supported metallocene catalyst system|
    US5238892A|1992-06-15|1993-08-24|Exxon Chemical Patents Inc.|Supported catalyst for 1-olefin polymerization|
    US5290745A|1992-08-10|1994-03-01|Union Carbide Chemicals & Plastics Technology Corporation|Process for producing ethylene polymers having reduced hexane extractable content|
    DE69307472T2|1992-11-10|1997-05-15|Mitsubishi Chem Corp|Process for the preparation of alpha-olefin polymers|
    US5332706A|1992-12-28|1994-07-26|Mobil Oil Corporation|Process and a catalyst for preventing reactor fouling|
    RU2120947C1|1993-04-26|1998-10-27|Эксон Кемикэл Пейтентс Инк.|Method of gas-phase polymerization in fluidized layer|
    ZA943399B|1993-05-20|1995-11-17|Bp Chem Int Ltd|Polymerisation process|
    FR2707651B1|1993-07-13|1995-08-25|Bp Chemicals Snc|Process for increasing the activity of a Ziegler-Natta type catalyst.|
    CA2127822A1|1993-07-13|1995-01-14|Yoshinori Morita|Process for gas phase polymerization of olefin|
    US5422325A|1993-09-17|1995-06-06|Exxon Chemical Patents Inc.|Supported polymerization catalysts, their production and use|
    US5518973A|1993-10-15|1996-05-21|Exxon Chemical Patents Inc.|Titanium trichloride catalyst system for polymerizing olefins|
    US5466649A|1993-10-15|1995-11-14|Exxon Chemical Patents Inc.|Polymerization catalyst systems, their production and use|
    EP0649992B1|1993-10-23|1997-07-30|WABCO GmbH|Disc brake actuator|
    JPH09505340A|1993-11-19|1997-05-27|エクソン・ケミカル・パテンツ・インク|Polymerization catalyst system, production method and use thereof|
    FI95276C|1993-12-03|1996-01-10|Borealis As|Catalyst for polymerization of olefins and process for their preparation|
    WO1995021874A1|1994-02-11|1995-08-17|Exxon Chemical Patents Inc.|Polymerization catalyst systems, their production and use|
    IT1269931B|1994-03-29|1997-04-16|Spherilene Srl|COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINE|
    US5629253A|1994-04-26|1997-05-13|Exxon Chemical Patents, Inc.|Polymerization catalyst systems, their production and use|
    WO1995030714A1|1994-05-09|1995-11-16|The Dow Chemical Company|Medium modulus film and fabrication method|
    IT1269837B|1994-05-26|1997-04-15|Spherilene Srl|COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINS|
    US5468702A|1994-07-07|1995-11-21|Exxon Chemical Patents Inc.|Method for making a catalyst system|
    US5643847A|1994-08-03|1997-07-01|Exxon Chemical Patents Inc.|Supported ionic catalyst composition|
    GB9417211D0|1994-08-25|1994-10-12|Solicitor For The Affairs Of H|Nucleotide sequencing method|
    US5525678A|1994-09-22|1996-06-11|Mobil Oil Corporation|Process for controlling the MWD of a broad/bimodal resin produced in a single reactor|
    KR100368194B1|1994-10-13|2003-04-03|니혼폴리올레핀 가부시키가이샤|A catalyst component for producing polyolefin, a catalyst for producing polyolefin containing the catalyst component, and a method for producing polyolefin in the presence of the catalyst|
    US5529965A|1994-10-28|1996-06-25|Exxon Chemical Patents Inc.|Polymerization catalyst systems, their production and use|
    US5625015A|1994-11-23|1997-04-29|Exxon Chemical Patents Inc.|Method for making supported catalyst systems and catalyst systems therefrom|
    US5714424A|1995-01-09|1998-02-03|W. R. Grace & Co.-Conn.|Multi-component polyolefin catalysts|
    IT1274253B|1995-02-21|1997-07-15|Himont Inc|PROCESS FOR THE PREPARATION OF SOLID CATALYTIC COMPONENTS FOR THE POLYMERIZATION OF OLEFINE|
    IT1275412B|1995-06-01|1997-08-05|Enichem Spa|PROCEDURE FOR THE PREPARATION OF MIXED POROUS SILICA-ALUMINUM OXIDES IN SPHERICAL FORM|
    US5569693A|1995-06-05|1996-10-29|Borden Inc.|High stretch film for pallet wrapping|
    CN1098283C|1995-07-06|2003-01-08|埃克森美孚化学专利公司|Method for producing prepolymerized supported metallocene catalyst system|
    US5677375A|1995-07-21|1997-10-14|Union Carbide Chemicals & Plastics Technology Corporation|Process for producing an in situ polyethylene blend|
    WO1997022639A1|1995-12-19|1997-06-26|Exxon Chemical Patents Inc.|High temperature solution polymerization process|
    EP0894005A1|1996-02-15|1999-02-03|The Board Of Governors For Higher Education State Of Rhode Island And Providence Plantations|Salmonella typhimurium vaccine|
    US5665818A|1996-03-05|1997-09-09|Union Carbide Chemicals & Plastics Technology Corporation|High activity staged reactor process|
    US5814399A|1996-03-12|1998-09-29|Tenneco Packaging|Stretch wrap films|
    US5998017A|1996-03-12|1999-12-07|Tenneco Packaging|Stretch wrap films|
    US5752362A|1996-03-12|1998-05-19|Tenneco Packaging|Stretch wrap films|
    US5749202A|1996-03-12|1998-05-12|Tenneco Packaging|Stretch wrap films|
    USRE38429E1|1996-03-12|2004-02-17|Tyco Plastics Services Ag|Stretch wrap films|
    US5902684A|1996-03-12|1999-05-11|Tenneco Packaging Inc.|Multilayered Metallocene stretch wrap films|
    US5627242A|1996-03-28|1997-05-06|Union Carbide Chemicals & Plastics Technology Corporation|Process for controlling gas phase fluidized bed polymerization reactor|
    US5723402A|1996-05-30|1998-03-03|Pq Corporation|Silicas with specific contents of cations as supports for olefin polymerization catalysts|
    US5747406A|1997-01-10|1998-05-05|Union Carbide Chemicals & Plastics Technology Corporation|Catalyst composition for the production of olefin polymers|
    EP0893454A4|1997-02-07|2001-01-24|Mitsui Chemicals Inc|Olefin polymerization catalyst and process for the production of olefin polymers|
    US6423420B1|1997-08-11|2002-07-23|Exxonmobil Chemical Patents Inc.|Oriented coextruded films|
    US6255426B1|1997-04-01|2001-07-03|Exxon Chemical Patents, Inc.|Easy processing linear low density polyethylene|
    US5889128A|1997-04-11|1999-03-30|Massachusetts Institute Of Technology|Living olefin polymerization processes|
    US6093480A|1997-05-21|2000-07-25|Tenneco Packaging|Stretch wrap films|
    US5907942A|1997-05-21|1999-06-01|Tenneco Packaging|Stretch wrap films|
    US5972510A|1997-06-05|1999-10-26|Isis Innovation Limited|Spherulite particles of isotactic polypropylene|
    US5907943A|1997-06-11|1999-06-01|Tenneco Packaging Inc.|Stretch wrap films|
    US5922441A|1997-06-11|1999-07-13|Tenneco Packaging Inc.|Stretch wrap films|
    US6103657A|1997-07-02|2000-08-15|Union Carbide Chemicals & Plastics Technology Corporation|Catalyst for the production of olefin polymers|
    US6083611A|1997-11-12|2000-07-04|Tenneco Packaging, Inc.|Roll wrap film|
    US6069213A|1997-12-16|2000-05-30|Union Carbide Chemicals & Plastics Technology Corporation|Mixed catalyst system|
    CN1293692B|1998-03-16|2010-06-09|陶氏环球技术公司|Polyolefin nanocomposites|
    PL343326A1|1998-03-26|2001-08-13|Dow Chemical Co|Ion exchanged aluminium-magnesium or fluorinated magnesium silicate aerogels and catalyst supports therefrom|
    BR9908171A|1998-03-27|2000-10-31|Exxon Chemical Patents Inc|Polymeric catalysts supported for olefin polymerization|
    IL138733D0|1998-04-06|2001-10-31|Borealis Tech Oy|High density polyethylene compositions, a process for the production thereof and films prepared thereof|
    US6333389B2|1998-12-18|2001-12-25|Univation Technologies, Llc|Olefin polymerization catalysts, their production and use|
    US6271325B1|1999-05-17|2001-08-07|Univation Technologies, Llc|Method of polymerization|
    US6265055B1|1999-10-13|2001-07-24|David Simpson|Multilayer stretch cling film|
    DE60021405T2|1999-10-22|2006-05-18|Univation Technologies, LLC, Houston|Catalyst systems and their use in a polymerisation process|
    BR0015235A|1999-10-22|2002-12-31|Univation Tech Llc|Catalyst compositions, polymerization methods, and polymers thereof|
    US6785287B1|1999-11-16|2004-08-31|Nokia Ip, Inc.|Integrated IP telephony and cellular communication system and method of operation|
    AU5859101A|2000-06-01|2001-12-11|Bp Chem Int Ltd|Novel polyethylene films|
    US6964937B2|2000-11-30|2005-11-15|Univation Technologies, Llc|Bimetallic catalyst for producing polyethylene resins with bimodal molecular weight distribution, its preparation and use|
    WO2002046246A2|2000-12-04|2002-06-13|Univaton Technologies, Llc|Polimerization process|
    US6518444B1|2000-12-18|2003-02-11|Univation Technologies, Llc|Preparation of polymerization catalysts|
    US6936675B2|2001-07-19|2005-08-30|Univation Technologies, Llc|High tear films from hafnocene catalyzed polyethylenes|
    CA2466612A1|2001-11-30|2003-06-12|Exxonmobil Chemical Patents Inc.|Bimetallic catalysts with higher activity|
    US6884748B2|2002-09-04|2005-04-26|Univation Technologies, Llc|Process for producing fluorinated catalysts|
    EP1537175B1|2002-09-05|2008-05-14|ExxonMobil Chemical Patents Inc.|Shrink film|
    AT494321T|2002-09-05|2011-01-15|Exxonmobil Chem Patents Inc|STRETCH FILM WINDING PROCESS|
    AU2003270780A1|2002-09-20|2004-04-08|Exxonmobil Chemical Patents Inc.|Polymer production at supercritical conditions|
    US6989344B2|2002-12-27|2006-01-24|Univation Technologies, Llc|Supported chromium oxide catalyst for the production of broad molecular weight polyethylene|
    US6958306B2|2003-08-28|2005-10-25|Univation Technologies, Llc|Activated catalyst systems from substituted dialuminoxane complexes|
    US7244795B2|2003-12-08|2007-07-17|Univation Technologies, Llc|Polymerization process using metallocene catalyst systems|
    CA2548324A1|2003-12-18|2005-07-21|Dow Global Technologies Inc.|Film with superior impact resistance and improved catastrophic failure resistance under high strain rate|
    US7741417B2|2004-01-07|2010-06-22|Exxonmobil Chemical Patents Inc.|Preparation of polymerization catalyst activators utilizing indole-modified silica supports|
    US7157531B2|2004-06-21|2007-01-02|Univation Technologies, Llc|Methods for producing polymers with control over composition distribution|
    US7741420B2|2004-07-14|2010-06-22|Exxonmobil Chemical Patents Inc.|Polymer production at supercritical conditions|
    US7169864B2|2004-12-01|2007-01-30|Novolen Technology Holdings, C.V.|Metallocene catalysts, their synthesis and their use for the polymerization of olefins|
    US7582711B2|2005-03-04|2009-09-01|Univation Technologies, Llc|Ziegler-type catalysts having increased productivity|
    US7951873B2|2006-05-05|2011-05-31|Exxonmobil Chemical Patents Inc.|Linear low density polymer blends and articles made therefrom|
    TWI404730B|2007-02-05|2013-08-11|Univation Tech Llc|Methods of controlling polymer properties|US9267918B2|2007-10-16|2016-02-23|Cambridge Enterprise Limited|Microfluidic systems|
    GB0720202D0|2007-10-16|2007-11-28|Cambridge Entpr Ltd|Microfluidic systems|
    EP2483334B1|2009-09-28|2016-08-24|ExxonMobil Chemical Patents Inc.|Polyolefin compositions and products made therefrom|
    US8975305B2|2012-02-10|2015-03-10|Kimberly-Clark Worldwide, Inc.|Rigid renewable polyester compositions having a high impact strength and tensile elongation|
    CN102796316A|2012-07-17|2012-11-28|太仓市鸿运包装材料有限公司|Red stretch film and production method thereof|
    CN102796309A|2012-07-17|2012-11-28|太仓市鸿运包装材料有限公司|Black stretch film and production method thereof|
    CN102796307A|2012-07-17|2012-11-28|太仓市鸿运包装材料有限公司|White winding membrane and production method thereof|
    CN102796310A|2012-07-17|2012-11-28|太仓市鸿运包装材料有限公司|Transparent winding film|
    CA2800056A1|2012-12-24|2014-06-24|Nova Chemicals Corporation|Polyethylene blend compositions|
    BR112015026427B1|2013-05-14|2020-07-21|Exxonmobil Chemical Patents Inc.|ethylene-based polymers and articles made of the same|
    WO2015187198A1|2014-06-06|2015-12-10|Kimberly-Clark Worldwide, Inc.|Hollow porous fibers|
    EP3060399A1|2013-10-16|2016-08-31|ExxonMobil Chemical Patents Inc.|Enhanced stretched cling performance polyolefin films|
    US11058791B2|2014-01-31|2021-07-13|Kimberly-Clark Worldwide, Inc.|Thin nanocomposite film for use in an absorbent article|
    CN105934466B|2014-01-31|2019-11-15|金伯利-克拉克环球有限公司|Nano combined packaging film|
    AU2015210792B2|2014-01-31|2019-04-18|Kimberly-Clark Worldwide, Inc.|Stiff nanocomposite film for use in an absorbent article|
    EP3152038B1|2014-06-06|2020-05-06|Kimberly-Clark Worldwide, Inc.|Thermoformed article formed from a porous polymeric sheet|
    CA2868640C|2014-10-21|2021-10-26|Nova Chemicals Corporation|Solution polymerization process|
    EP3209722A2|2014-10-21|2017-08-30|Nova ChemicalsS.A.|Ethylene interpolymer product with dilution index|
    CN105524339B|2014-10-27|2017-09-29|中国石油化工股份有限公司|A kind of polyethylene film|
    BR102015027108B1|2014-10-27|2021-01-12|China Petroleum & Chemical Corporation|polyethylene composition and film|
    GB2549412B8|2014-11-26|2021-07-07|Kimberly Clark Co|Annealed porous polyolefin material|
    WO2016122621A1|2015-01-30|2016-08-04|Kimberly-Clark Worldwide, Inc.|Film with reduced noise for use in an absorbent article|
    AU2015380470A1|2015-01-30|2017-08-10|Kimberly-Clark Worldwide, Inc.|Absorbent article package with reduced noise|
    WO2017070925A1|2015-10-30|2017-05-04|Dow Global Technologies Llc|Infrared absorbing, heat retaining film|
    CN109476881B|2016-07-27|2021-07-02|Sabic环球技术有限责任公司|Polyethylene composition|
    BR112019006076A2|2016-09-29|2019-06-18|Dow Global Technologies Llc|multilayer stretching films and methods thereof|
    CN110023353A|2016-12-16|2019-07-16|陶氏环球技术有限责任公司|Ethylene/alpha-olefin interpolymers composition|
    BR112019011290A2|2016-12-19|2019-10-15|Dow Global Technologies Llc|driver's shirt and process to produce the same|
    US10329412B2|2017-02-16|2019-06-25|Nova ChemicalsS.A.|Caps and closures|
    US10442920B2|2017-04-19|2019-10-15|Nova ChemicalsS.A.|Means for increasing the molecular weight and decreasing the density of ethylene interpolymers employing homogeneous and heterogeneous catalyst formulations|
    WO2019022801A1|2017-07-24|2019-01-31|Exxonmobil Chemical Patents Inc.|Polyethylene films and methods od making the same|
    KR102351569B1|2017-12-18|2022-01-14|주식회사 엘지화학|Polyethlene resin film|
    CN112739732A|2018-12-21|2021-04-30|Lg化学株式会社|Polyolefins|
    US10882987B2|2019-01-09|2021-01-05|Nova ChemicalsS.A.|Ethylene interpolymer products having intermediate branching|
    US11046843B2|2019-07-29|2021-06-29|Nova ChemicalsS.A.|Ethylene copolymers and films with excellent sealing properties|
    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-07-30| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-01-28| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-03-17| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 22/03/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US32360110P| true| 2010-04-13|2010-04-13|
    US61/323,601|2010-04-13|
    PCT/US2011/029422|WO2011129956A1|2010-04-13|2011-03-22|Polymer blends and films made therefrom|
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