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    • 专利摘要:
    polymer films having improved heat sealing properties a polymer composition comprising an ethylene alpha-olefin copolymer, wherein the polymer composition is characterized as having (a) a density in the range of greater than about 0.910 g / cm³ at about 0.930 g / cm³, as determined according to astm d1505; (b) a melting index in the range of greater than about 0.5 g / 10 min to about 3 g / 10 min, as determined by astm d1238, condition 190 ºc / 2.16 kg; (c) a molecular weight distribution of about 3.4 to about 12, as determined by gel permeation chromatography (gpc); (d) a weight average molecular weight greater than about 85 kg / mol to about 160 kg / mol, as determined by gel permeation chromatography (gpc); and (e) average molecular weight z greater than about 210 kg / mol to about 500 kg / mol, as determined by gel permeation chromatography (gpc).
    公开号:BR112015022786B1
    申请号:R112015022786-4
    申请日:2014-03-06
    公开日:2020-08-18
    发明作者:Chung C. Tso；Albert P. Masino；Ashish M. Sukhadia
    申请人:Chevron Phillips Chemical Company Lp；
    IPC主号:
    专利说明:

    CROSS REFERENCE FOR RELATED ORDERS
    [001] Not applicable. TECHNICAL FIELD
    [002] This disclosure refers to new polymers. More specifically, this disclosure refers to new polymers having improved thermal properties. FUNDAMENTALS
    [003] Polyolefins are plastic materials useful for preparing a wide variety of valuable products due to their combination of rigidity, ductility, barrier properties, temperature resistance, optical properties, availability and low cost. One of the most valued products is plastic film. In particular, polyethylene (PE) is one of the most widely consumed polymers in the world. It is a versatile polymer that offers high performance compared to other polymers and alternative materials such as glass, metal or paper. Plastic films like PE films are mainly used in packaging applications, but they also find use in the agricultural, medical and engineering fields.
    [004] PE films are manufactured in a variety of grades that are generally differentiated by polymer density so that PE films can be designated, for example, low density polyethylene (LDPE), linear low density polyethylene (LLDPE) , medium density polyethylene (MDPE) and high density polyethylene (HDPE) in which each density range has a unique combination of properties making them suitable for a particular application.
    [005] Thermal sealing is the main technique used to form and close flexible packages. Heat is used to quickly activate a sealing layer composed of a heat sealable material, usually a polymeric material. The temperature required to activate the heat sealable material and form a durable seal is called the seal start temperature (SIT) and the seal's ability to resist opening immediately after it is formed is called hot adhesion. The temperature range over which a durable seal can be formed and maintained is called the hot adhesion window while the resistance of the formed seal is called the resistance of the thermal seal.
    [006] A factor in the use of these polymers as sealants is the thermal property of the materials. Thus, a continuing need exists for polymers (for example, PE) having improved thermal properties. SUMMARY
    [007] A polymer composition comprising an alpha-olefin ethylene copolymer is disclosed herein wherein the polymer composition is characterized as having (a) a density in the range of greater than about 0.910 g / cm3 to about 0.930 g / cm3, as determined according to ASTM D1505; (b) a melt index in the range of greater than about 0.5 g / 10 min to about 3 g / 10 min. as determined according to ASTM D1238, Condition 190 ° C / 2.16 kg; (c) a molecular weight distribution of about 3.4 to about 12, as determined by gel permeation chromatography; (d) a weight average molecular weight greater than about 85 kg / mol to about 160 kg / mol, as determined by gel permeation chromatography; and (e) average molecular weight z greater than about 210 kg / mol to about 500 kg / mol, as determined by gel permeation chromatography.
    [008] Also disclosed here is a manufactured film article comprising a polymer composition comprising an alpha-olefin copolymer of ethylene, wherein the polymer composition is characterized as having (a) a density in the range of greater than about 0.910 g / cm3 to about 0.930 g / cm3, as determined according to ASTM D1505 (b) a melt index in the range of greater than about 0.5 g / 10 min to about 3 g / 10 min as determined from according to ASTM D1238, Condition 190 ° C / 2.16 kg (c) a molecular weight distribution of about 3.4 to about 12, as determined by gel permeation chromatography (d) a higher average weight molecular weight than about 85 kg / mol to about 160 kg / mol, as determined by gel permeation chromatography and (e) average molecular weight z greater than about 210 kg / mol to about 500 kg / mol, as determined by gel permeation chromatography so that the film article made from the polymer composition is characterized as having a hot tack initiation temperature of less than about 96 ° C, as determined according to ASTM F1921- 98, method A.
    [009] Also disclosed here is a manufactured film article comprising a polymer composition comprising an alpha-olefin ethylene copolymer in which the polymer composition is characterized as having (a) a density in the range of greater than about 0.910 g / cm3 at about 0.930 g / cm3, as determined according to ASTM D1505 (b) a melt index in the range of greater than about 0.5 g / 10 min to about 3 g / 10 min, as determined from according to ASTM D1238, Condition 190 ° C / 2.16 kg (c) a molecular weight distribution of about 3.4 to about 12, as determined by gel permeation chromatography (d) a higher average weight molecular weight than about 85 kg / mol to about 160 kg / mol, as determined by gel permeation chromatography and (e) average molecular weight z greater than about 210 kg / mol to about 500 kg / mol, as determined by gel permeation chromatography so that the film article made from the polymer composition is characterized as having (i) a hot tack initiation temperature of less than about 96 ° C, as determined according to ASTM F1921-98, method A and (ii) a hot tack initiation temperature range greater than about 20 ° C, as determined according to ASTM F1921-95, method A. BRIEF DESCRIPTION OF THE DRAWINGS
    [0010] For a more complete understanding of this disclosure and its advantages, now refer to the following brief description, taken in connection with the accompanying figures and detailed description, in which equal reference numbers represent equal parts.
    [0011] Figure 1 is a representation of an analytical temperature raising the elution fraction profile for a polymer of the type disclosed here.
    [0012] Figure 2 is a graph of the hot tack initiation temperature as a function of the resin density for the indicated samples.
    [0013] Figure 3 is a graph of the hot tack initiation temperature range as a function of the hot tack initiation temperature for the indicated samples.
    [0014] Figures 4 and 5 are elution fractionation profiles of analytical temperature rise for the samples of example 1. DETAILED DESCRIPTION
    [0015] Polymers having improved thermal properties and methods for preparing and using them are disclosed here. Here, the polymer refers to both a material collected as a product of a polymerization reaction (for example, a reactor or virgin resin) and a polymeric composition comprising a polymer and one or more additives. In one embodiment, a monomer (for example, ethylene) can be polymerized using the methodologies disclosed here to produce a polymer of the type disclosed here.
    [0016] In one embodiment, polymers of the type disclosed here are characterized as polymers catalyzed by metallocene having improved thermal properties and called PITs. In one embodiment, the polymer is a linear low density polyethylene. Several characteristics and properties of PITs are disclosed here.
    [0017] In one embodiment, a PIT of the type described here can be prepared by any suitable methodology, for example, using one or more catalyst systems, in one or more reactors, in solution, in paste or in gas phase, and / or varying the concentration of the monomer in the polymerization reaction, and / or changing all / any materials or parameters involved in the production of the PITs, as will be described in more detail later here.
    [0018] The PIT of the present disclosure can be produced using various types of polymerization reactors. As used herein, "polymerization reactor" includes any reactor capable of polymerizing olefin monomers to produce homopolymers and / or copolymers. Homopolymers and / or copolymers produced in the reactor can be referred to as resin and / or polymers. The various types of reactors include, among others, those that can be referred to as batch, paste, gas phase, solution, high pressure, tubular, autoclave, or other reactor and / or reactors. Gas phase reactors can comprise fluidized bed reactors or horizontal phase reactors. Paste reactors may comprise vertical and / or horizontal handles. High pressure reactors may comprise autoclave and / or tubular reactors. Reactor types can include batch and / or continuous processes. Continuous processes can use intermittent and / or continuous product download or transfer. The processes may also include partial or complete direct recycling of unreacted monomer, unreacted comonomer, catalyst and / or cocatalysts, diluents and / or other polymerization process materials.
    [0019] Polymerization reactor systems of the present disclosure may comprise one type of reactor in a system or several reactors of the same or different type, operated in any suitable configuration. The production of polymers in multiple reactors can include several phases in at least two separate polymerization reactors, interconnected by a transfer system, making it possible to transfer the polymers resulting from the first polymerization reactor in the second reactor. Alternatively, polymerization in multiple reactors may include the transfer, manually or automatically, of polymer from one reactor to reactor or subsequent reactors for further polymerization. Alternatively, multi-phase or multi-stage polymerization can take place in a single reactor, where conditions are changed so that a different polymerization reaction occurs.
    [0020] The desired polymerization conditions in one of the reactors may be the same or different from the operating conditions of any other reactors involved in the entire polymer production process of the present disclosure. Various reactor systems may include any combination, including but not limited to, several loop reactors, multiple gas phase reactors, a combination of loop and gas phase reactors, multiple high pressure reactors or a combination of high pressure reactors pressure with handle and / or gas. The various reactors can be operated in series or in parallel. In one embodiment, any arrangement and / or any combination of the reactors can be employed to produce the polymer of the present disclosure.
    [0021] According to one embodiment, the polymerization reactor system may comprise at least one loop paste reactor. These reactors can comprise vertical or horizontal loops. Monomer, diluent, catalyst system and, optionally, any comonomer can be continuously fed to a loop paste reactor, where polymerization takes place. Generally, continuous processes may comprise the continuous introduction of a monomer, a catalyst, and / or a diluent into a polymerization reactor and the continuous removal of this reactor from a suspension comprising polymer particles and the diluent. The effluent from the reactor may be evaporated to remove liquids comprising the solid polymer, monomer and / or comonomer diluent. Various technologies can be used for this separation step including, but not limited to, vaporization which can include any combination of heat addition and pressure reduction, separation by cyclonic action on a cyclone or hydrocyclone, or separation by centrifugation; or other appropriate separation methods.
    [0022] Typical pulp polymerization processes (also known as particle shape processes) are disclosed in US Patents 3,248,179, 4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191 and 6,833. 415, for example; each of which are incorporated here as a reference in their entirety.
    [0023] Suitable diluents used in the polymerization of paste include, among others, the monomer being polymerized and hydrocarbons that are liquid under reaction conditions. Examples of suitable diluents include, but are not limited to, hydrocarbons such as propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane and n-hexane. Some loop polymerization reactions can occur under bulk conditions where no thinner is used. An example is polymerization of the propylene monomer as disclosed in US Patents 5,455,314, which is incorporated by reference in its entirety.
    [0024] According to another embodiment, the polymerization reactor can comprise at least one gas phase reactor. These systems can employ a continuous recycling stream that contains one or more monomers continuously recycled through a fluidized bed in the presence of catalyst under polymerization conditions. A recycling stream can be removed from the fluidized bed and recycled back to the reactor. Simultaneously, the polymer product can be removed from the reactor and new or fresh monomer can be added to replace the polymerized monomer. These gas phase reactors can comprise a process for multi-stage polymerization of olefin gas phase, in which olefins are polymerized in the gas phase in at least two independent gas phase polymerization zones while feeding a polymer containing catalyst formed in a first polymerization zone to a second polymerization zone. A type of gas phase reactor is disclosed in US Patents 4,588,790, 5,352,749, and 5,436,304, each of which is incorporated herein by reference in its entirety.
    [0025] According to yet another modality, a high pressure polymerization reactor can comprise a tubular reactor or an autoclave reactor. Tubular reactors can have several zones where fresh monomer, initiators, or catalysts are added. The monomer can be entrained in an inert gas stream and introduced into a zone of the reactor. Primers, catalysts and / or catalyst components can be entrained in a gaseous stream and introduced into another zone of the reactor. Gaseous streams can be mixed for polymerization. Heat and pressure can be used properly to obtain optimal polymerization reaction conditions.
    [0026] Still according to another modality, the polymerization reactor can comprise a solution polymerization reactor in which the monomer is contacted with the catalyst composition by proper stirring or other means. A carrier comprising an excess organic diluent or monomer can be employed. If desired, the monomer can be brought in the vapor phase in contact with the catalytic reaction product, in the presence or absence of liquid material. The polymerization zone is maintained at temperatures and pressures that will result in the formation of a polymer solution in a reaction medium. Stirring can be used to obtain the best temperature control and to maintain uniform polymerization mixes throughout the polymerization zone. Suitable means are used to dissipate the exothermic heat from polymerization.
    [0027] Polymerization reactors suitable for the present disclosure may further comprise any combination of at least one feedstock feed system, at least one feedstock for catalyst or catalyst components, and / or at least one recovery system polymer. Reactor systems suitable for the present disclosure may also comprise systems for purification of raw material, storage and preparation of catalyst, extrusion, refrigeration reactor, polymer recovery, fractionation, recycling, storage, unloading, laboratory analysis and process control.
    [0028] Conditions that are controlled for polymerization efficiency and to provide the properties of the polymer include, among others, temperature, pressure, type and amount of catalyst or cocatalyst and the concentrations of various reagents. The polymerization temperature can affect catalyst productivity, polymer molecular weight and molecular weight distribution. Suitable polymerization temperatures can be any temperature below the depolymerization temperature, according to the Gibbs free energy equation. This typically includes about 60 ° C to about 280 ° C, for example, and / or about 70 ° C to about 110 ° C, depending on the type of polymerization reactor and / or polymerization process.
    [0029] Appropriate pressures will also vary according to the reactor and polymerization process. The pressure for liquid phase polymerization in a loop reactor is typically less than 1000 psig. The pressure for gas phase polymerization is generally about 200 - 500 psig. High pressure polymerization in tubular or autoclave reactors is generally performed at about 20,000 to 75,000 psig. Polymerization reactors can also be operated in a supercritical region, generally occurring at higher temperatures and pressures. Operating above the critical point of a pressure / temperature diagram (supercritical phase) can offer advantages.
    [0030] The concentration of various reagents can be controlled to produce polymers with certain physical and mechanical properties. The proposed end-use product that will be formed by the polymer and the method for forming that product can be varied to determine the desired final product properties. Mechanical properties include, but are not limited to, tensile strength, flexural modulus, impact resistance, creep, stress relaxation and hardness tests. Physical properties include, but are not limited to, density, molecular weight, molecular weight distribution, melting temperature, glass transition temperature, crystallization melting temperature, density, stereoregularity, crack growth, short chain branching, long chain branching, and rheological measurements.
    [0031] The concentrations of monomer, comonomer, hydrogen, cocatalyst, modifiers, and electron donors are generally important in the production of specific polymer properties. The comonomer can be used to control the density of the product. The hydrogen can be used to control the molecular weight of the product. Cocatalysts can be used to alkylate, eliminate poisons and / or control molecular weight. The concentration of poisons can be minimized, as poisons can affect reactions and / or otherwise affect the properties of the polymer product. Modifiers can be used to control product properties and electron donors can affect stereoregularity.
    [0032] In one embodiment, a method for preparing a PIT comprises contacting an olefin monomer (for example, ethylene) with a catalyst system under conditions suitable for the formation of a polymer of the type described here. In one embodiment, the catalyst system comprises a transition metal complex. The terms "catalyst composition", "catalyst mixture", "catalyst system" and the like, do not depend on the actual product resulting from contact or reaction of the components of the mixtures, the nature of the active catalytic site, or the fate of the cocatalyst, the catalyst, any olefin monomer used to prepare a pre-contacted mixture, or the activator-support, after combining these components. Therefore, the terms "catalyst composition", "catalyst mixture", "catalyst system" and the like, can include both heterogeneous compositions and homogeneous compositions.
    [0033] In one embodiment, a catalyst system suitable for the preparation of a PIT comprises at least one compound containing metallocene. In one embodiment, the metallocene-containing compound is a bridged metallocene, designated MTE-A. Here, the term "metallocene" describes a compound comprising at least one cycloalkadienyl-like fraction η3 to η5, in which cycloalkadienyl fractions η3 to η5 include cyclopentadienyl linkers , indenyl binders, fluorenyl binders, and the like, including partially saturated or substituted derivatives or analogues of any of these. Possible substituents on these binders include hydrogen, therefore, the description "substituted derivatives thereof" in this disclosure comprises partially saturated binders such as tetrahydroindenyl, tetrahydrofluorenyl, octahidrofluorenyl, partially saturated indenyl, partially saturated fluorenyl, partially saturated substituted fluorenyl, and the like .
    [0034] In one embodiment, MTE-A is a compound that can be characterized by one of the general formulas 1 or 2:

    where each X is independently F, Cl, Br, I, methyl, benzyl, phenyl, H BH4, a hydrocarbiloxide group having up to 20 carbon atoms, a hydrocarbilamino group having up to 20 carbon atoms, a trihydrocarbylsilyl group having up to 20 atoms carbon, OBR'2 where R 'can be an alkyl group having up to 12 carbon atoms or an aryl group having up to 12 carbon atoms and SO3R ", where R" can be an alkyl group having up to 12 carbon atoms or an aryl group having up to 12 carbon atoms; Y is a CR2 or SiR2 group where R is hydrogen or a hydrocarbyl group; CpA, CpB, Cpc, and CpD are each independently a substituted or unsubstituted cyclopentadienyl group, indenyl group, or flourenyl group and where any substituted CpA, CpB, Cpc, and CpD can be H, a hydrocarbon group having up to 18 carbon atoms or a hydrocarbylsilyl group having up to 18 carbon atoms.
    [0035] Non-limiting examples of metallocene-containing compounds suitable for use in this disclosure are described in more detail in US Patents 4,939,217; 5,191,132; 5,210,352; 5,347,026; 5,399,636; 5,401,817; 5,420,320; 5,436,305; 5,451,649; 5,496,781; 5,498,581; 5,541,272; 5,554,795; 5,563,284; 5,565,592; 5,571,880; 5,594,078; 5,631,203; 5,631,335; 5,654,454; 5,668,230; 5,705,478; 5,705,579; 6,187,880; 6,509,427; 7,026,494, and US Patent Applications 20100190926 A1 and 20120059134, each of which is incorporated herein by reference in its entirety.
    [0036] In an alternative embodiment, the metallocene-containing compound comprises a bridged metallocene compound referred to as MTE-B. In one modality, MTE-B can use one of the general formulas 3 or 4:

    where M is Ti, Zr or Hf; each X is independently F, Cl, Br, I, methyl, benzyl, phenyl, H BH4, a hydrocarbiloxide group having up to 20 carbon atoms, a hydrocarbilamino group having up to 20 carbon atoms, a trihydrocarbylsilyl group having up to 20 carbon atoms , OBR'2 where R 'can be an alkyl group having up to 12 carbon atoms or an aryl group having up to 12 carbon atoms, or SO3R ", where R" can be an alkyl group having up to 12 carbon atoms or an aryl group having up to 12 carbon atoms; Y is a CR2 SiR2 or R2CCR2 group that can be linear or cyclic where R is hydrogen or a hydrocarbyl group; CpA, CpB, Cpc, and CpD are each independently a substituted or unsubstituted cyclopentadienyl group, indenyl group, or flourenyl group and where any substituent on CpA, CpB, Cpc, and CpD can be H, a hydrocarb group having up to 18 atoms carbon or a hydrocarbylsilyl group having up to 18 carbon atoms. E represents a bridge group that can comprise (i) a cyclic or heterocyclic fraction having up to 18 carbon atoms, (ii) a group represented by the general formula EAR3AR4A, where EA is C, Si, Ge or B, and R3A and R4A are independently H or a hydrocarbon group having up to 18 carbon atoms, (iii) a group represented by the general formula —CR3BR4B — CR3CR4C—, where R3B, R4B, R3C, and R4C are independently H or a hydrocarbon group having up to 10 carbon atoms, or (iv) a group represented by the general formula SÍR2-CR2 where X is Si or C and R is a hydrogen or hydrocarbyl group; or —SiR3DR4D — SiR3ER4E—, where R3D, R4D, R3E, and R4E are independently H or a hydrocarbon group having up to 10 carbon atoms, and at least one of R3A, R3B, R4A, R4B, R3C, R4C, R3D, R4D, R3E, R4E or the substituent on Cp, Cpi, or Cp2, is (1) a terminal alkenyl group having up to 12 carbon atoms or (2) a dinuclear compound in which each metal fraction has the same structural characteristic of MTE-B. In some embodiments, the catalyst comprises at least two compounds containing metallocene of the type disclosed herein.
    [0037] The PIT can comprise additives. Examples of additives include, but are not limited to, antistatic agents, dyes, stabilizers, nucleators, surface modifiers, pigments, glidants, anti-blocking agents, adhesion promoters, polymer processing aids, and combinations thereof. These additives can be used singly or in combination and can be contacted with the polymer before, during or after the preparation of the PIT as described here. These additives can be added by any suitable technique, for example, during an extrusion or composition step as during pelletizing or subsequent processing on an end-use article.
    [0038] In one embodiment, the PIT comprises polyethylene, for example, metallocene-catalyzed polyethylene. In one embodiment, the PIT comprises a polyethylene homopolymer, for example, a metallocene-catalyzed polyethylene homopolymer. It should be understood that an insignificant amount of comonomer may be present in the polymers disclosed herein and the polymer is still considered a homopolymer. Here, an insignificant amount of a comonomer refers to an amount that does not substantially affect the properties of the polymer disclosed herein. For example, a comonomer can be present in an amount of less than about 1.0% by weight 0.5% by weight, 0.1% by weight or 0.01% by weight based on the total weight of the polymer.
    [0039] In an alternative embodiment, the PIT comprises a polyethylene copolymer, also called an ethylene (alpha-olefin) copolymer, for example, a metallocene-catalyzed polyethylene copolymer. Examples of suitable comonomers include, but are not limited to, unsaturated hydrocarbons having 3 to 20 carbon atoms such as propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, and mixtures thereof.
    [0040] In one embodiment, the PIT has a weight average molecular weight (Mw) of about 80 kg / mol to about 170 kg / mol, alternatively from about 85 kg / mol to about 145 kg / mol, alternatively from about 90 kg / mol to about 140 kg / mol, or alternatively from about 85 kg / mol to about 160 kg / mol. In one embodiment, PIT has a numerical average molecular weight (Mn) of about 7 kg / mol to about 50 kg / mol, alternatively from about 9 kg / mol to about 35 kg / mol, or alternatively about from 10 kg / mol to about 32 kg / mol. In one embodiment, PIT has an average molecular weight z (Mz) of greater than about 210 kg / mol to about 500 kg / mol, alternatively from about 220 kg / mol to about 470 kg / mol, or alternatively from about 230 kg / mol to about 450 kg / mol. The weight average molecular weight can be calculated according to equation 1:
    where Ni is the number of molecules with molecular weight Mi. All molecular weight averages are expressed in kilograms per mol (kg / mol) or kiloDalton and are determined by gel permeation chromatography. The numerical average molecular weight is the common average of the molecular weights of the individual polymers and can be calculated according to equation (2):
    The average molecular weight z is a high-order molecular weight average that is calculated according to equation (3)
    where n ± is the amount of substance of the species ie Mi is the molar mass of the species.
    [0041] The PIT can still be characterized by a molecular weight distribution (MWD) greater than or equal to 3.3, alternatively from about 3.4 to about 12, alternatively from about 3.5 to about 11, or alternatively from about 3.6 to about 10. MWD refers to the ratio of Mw to Mn, which is also called polydispersity index (PDI), or more simply polydispersity.
    [0042] In one embodiment, PIT is characterized as a substantially linear polymer having less than about 22 branches per 1000 carbon atoms, alternatively less than about 20 branches per 1000 carbon atoms or alternatively less than about 19 branches per 1000 carbon atoms.
    [0043] The PIT can be characterized as having a density of less than about 0.945 g / cm3, alternatively from about 0.910 g / cm3 to about 0.940 g / cm3, alternatively from about 0.912 g / cm3 to about 0.935 g / cm3, alternatively from about 0.913 g / cm3 to about 0.925 g / cm3, or alternatively greater than about 0.910 g / cm3 to about 0.930 g / cm3 as determined according to ASTM D 1505.
    [0044] The PIT can be characterized as having a melt index (MI) greater than about 0.5 g / 10 min. at about 3.0 g / 10 min., alternatively about 0.6 g / 10 min. at about 2.5 g / 10 min., or alternatively about 0.7 g / 10 min. at about 2.0 g / 10 min. MI refers to the amount of a polymer that can be forced through a 0.0825 inch diameter extrusion rheometer orifice when subjected to a force of 2.16 kg in ten minutes at 190 ° C, as determined by according to ASTM D 1238.
    [0045] The PIT can be characterized as having a high charge melt index (HLMI) of about 10 g / 10 min. at about 28 g / 10 min., alternatively about 11 g / 10 min. at about 27 g / 10 min., or alternatively about 12 g / 10 min. at about 26 g / 10 min. HLMI refers to the amount of a polymer that can be forced through a 0.0825 inch diameter extrusion rheometer orifice when subjected to a force of 21.6 kg in ten minutes at 190 ° C, as determined by according to ASTM D 1238.
    [0046] The PIT can be characterized as having an HLMI to MI ratio of about 16 to about 30, alternatively from about 16.5 to about 28 or alternatively from about 17 to about 26.
    [0047] In one embodiment, the PIT has a zero shear viscosity value, Eta (0), from about 3000 Pa.s to about 25000 Pa.s, alternatively from about 4000 Pa.s to about 20000 Pa. s, or alternatively about 5000 Pa.s to about 18000Pa.s when the dynamic complex viscosity versus the frequency sweep are adjusted for Carreau-Yasuda, equation (4), with a value of n = 0.1818:
    E = viscosity (Pa-s) Y = shear rate (1 / s) a = rheological width parameter T = relaxation time (s) [describes the transition region] Eo = zero Newtonian plateau shear viscosity] n = Power law constant [defines the final slope of the high shear rate region]
    [0048] To facilitate the assembly of the model, the constant of the Power n law is kept at a constant value. Details of the meaning and interpretation of the CY model and derived parameters can be found at: C. A. Hieber and H. H. Chiang, Rheol. Acta, 28, 321 (1989); C.A. Hieber and H.H. Chiang, Polym. Eng. Sci., 32, 931 (1992); and R. B. Bird, R. C. Armstrong and 0. Hasseger, Dynamics of Polymeric Liquids, Volume 1, Fluid Mechanics, 2nd Edition, John Wiley & Sons (1987), each of which is defined here as a reference in its entirety.
    [0049] The zero shear viscosity refers to the viscosity of the polymeric composition at a zero shear rate and is indicative of the molecular structure of materials. In addition, for polymer fusions, zero shear viscosity is often a useful indicator of processing attributes such as the melt strength of polymer fusions in polymer processes. For example, the higher the zero shear viscosity, the better the melt strength.
    [0050] In one embodiment, the PIT has a Carreau-Yasuda "a" value of about 0.400 to about 0.680, alternatively from about 0.420 to about 0.650, or alternatively from about 0.450 to about 0.630 where the dynamic complex viscosity versus frequency sweep are adjusted for the Carreau-Yasuda equation with value n = 0.1818.
    [0051] In one embodiment, a PIT of the type disclosed here is characterized by an elution fractionation profile of analytical temperature rise (ATREF) of the type shown in Figure 1, or alternatively substantially similar to the same. To generate an ATREF profile, a sample of the polymer to be analyzed is dissolved in a suitable hot solvent (for example, trichlorobenzene) and crystallized in a column containing an inert support (stainless steel shot), slowly, reducing the temperature. The column is usually equipped with a refractive index detector and a differential viscometer detector. An ATREF chromatogram curve is then generated by eluting the sample of the column crystallized polymer by slowly increasing the temperature of the elution solvent (trichlorobenzene). In one embodiment, the elution fractionation temperature range for a polymer of the type disclosed here (i.e., PIT) is about 20 ° C to about 110 ° C; alternatively from about 20 ° C to about 108 ° C or alternatively from about 20 ° C to about 105 ° C.
    [0052] Referring to Figure 1, a PIT of the type disclosed here may present an ATREF profile which is a graph of the molecular weight characteristics of the polymer (for example, dW / dT) as a function of temperature containing at least two components that elute at different temperatures, resulting in at least two peaks, called peak A, PA, and peak B, PB. Here, the elution temperature corresponds to a peak observed on an ATREF curve as determined from the temperature increasing from the elution fraction in the range of about 20 ° C to about 110 ° C. A peak observed in the ATREF profile corresponds to a substantial weight percentage of a crystallized polymer portion based on the total amount of crystallizable polymer portions for the polymer as a whole. Polymers of the types disclosed herein (i.e., PITs) with crystallizable polymer portions can be characterized as having measurable crystallized polymer portions at several different peak temperatures (i.e., multiple peaks). In one embodiment, an ATREF profile of the type disclosed here comprises two measurable crystallized polymer portions that add up to more than about 90%, alternatively 91, 92, 93, 94, 95, 96, 97, 98 or 99% of the polymer portions crystallisable present in the polymer as a whole. It is contemplated that additional peaks (for example, shoulders, humps and doublets) may be present in the ATREF profile of a polymer of the type disclosed here. Alternatively, additional peaks can also be present between the lowest temperature peak and the highest temperature peak, in which case the lowest temperature peak should be designated as PA and the highest temperature peak should be designated as PB.
    [0053] In one embodiment, PA has an elution temperature designated TA θ PB has an elution temperature designated TB where the difference between TA and TB, designated Δ, is equal to more than about 23, alternatively from about 23 to about 35, or alternatively about 23 to about 33.
    [0054] In one embodiment, a PIT is made into a film. The films for this promotion can be produced using any suitable methodology. In one embodiment, polymers (ie PITs) are formed into films through a film blowing process. In one embodiment, blown film samples can be prepared using the following conditions: diameter of 100 mm (4 inches) of die, gap of 1.5 mm (0.060 inch) of die, single screw extruder of 3 7.5 mm (1.5 inches) in diameter equipped with a barrier screw with a Maddock mixing section at the end (L / D = 24, compression ratio 2.2: 1), screw speed of 115 RPM [about 27 kg / h (60 lb / h) exit rate], blowing rate (BUR) 2.5: 1 (BUR), bubble "in the pocket" with "freezing line height" (FLH) between 2 0 and 28 cm (8-11 inches), set barrel and die temperatures at 190 ° C (375 ° F) 1m film thickness (25 microns). Cooling can be performed with a Dual Lip air ring using ambient (laboratory) air at about 25 ° C (75-80 ° F).
    [0055] The films formed from polymers of this disclosure (ie, PITs) can be of any thickness desired by the user. Alternatively, PIT can be formed into a film having a thickness of about 0.1 mil to about 5 mil, alternatively from about 0.2 mil to about 4.0 mil, alternatively from about 0.3 ml to about 3.0 thousand.
    [0056] In one embodiment, the films formed from the PITs of that disclosure have a resistance to dart fall ranging from about 500 g / thousand to about 2000 g / thousand, alternatively from about 700 g / thousand to about 1700 g / mil or alternatively from about 900 g / mil to about 1400 g / mil, as measured in accordance with ASTM DI709 Method A using a blown film test sample having a thickness of 1.0 mil. Dart drop resistance refers to the weight required to cause 50% of tested films to fail due to the impact of a dart falling under specified test conditions. Specifically, a method employs the use of a dart having a head diameter of 38 mm (1.5 in.) That falls from a height of 0.66 m (26.1 in.).
    [0057] In one embodiment, the films formed from the PITs of this disclosure have an Elmendorf rupture resistance in the machine direction (MD) of about 70 g / mil to about 300 g / mil, alternatively about 90 g / mil at about 250 g / mil, or alternatively from about 100 g / mil to about 200 g / mil and an Elmendorf tear strength in the transverse direction (TD) ranging from about 250 g / mil to about 650 g / mil mil, alternatively from about 280 g / mil to about 550 g / mil, or alternatively from about 300 g / mil to about 500 g / mil as measured according to ASTM D1922 using a blown film test sample with a thickness of 1.0 mil.
    [0058] In one embodiment, films formed from PITs of the type disclosed here have a Seal Initiation Temperature (SIT) of about 85 ° C to about 105 ° C, alternatively from about 88 ° C to about 103 ° C or alternatively about 89 ° C to about 100 ° C, a Hot Stick Initiation Temperature (HTIT) less than about 100 ° C, alternatively less than about 96 ° C, alternatively less than about 95 ° C, alternatively less than about 93 ° C and a Hot Stick Temperature Range (HTR) greater than about 20 ° C, alternatively greater than about 23 ° C, or alternatively greater than about 25 ° C . Here, SIT refers to the temperature at which the sealed film product reaches a seal strength of 0.3 lb / in, HTIT refers to the temperature at which the hot tack resistance is equal to or greater than 0.225 lb / in. in and HTR refers to the temperature range in which the hot bond strength is equal to or greater than 0.225 lb / in. The HTR is determined by subtracting the lowest temperature at which 0.225 lb / in hot adhesion strength is achieved by the highest temperature at which 0.225 lb / in hot adhesion resistance is achieved using the hot versus temperature resistance curve. The SIT and hot tack window can be determined using a heat seal tester in accordance with ASTM F 1921-98 method A.
    [0059] PITs of the type disclosed here can be formed into articles of manufacture or articles of end use using any suitable methodology such as extrusion, blow molding, injection molding, fiber spinning, thermoforming and molding. For example, PIT can be extruded into a sheet which is then thermoformed into an end-use article such as a container, cup, tray, pellet, toy or component from another product. EXAMPLE 1
    [0060] The heat sealing properties of the PITs of the type disclosed here have been investigated. Specifically, the sealing properties were determined as follows: using a Theller Engineering Heat Seal Test System (Method A for Hot Adhesion and Heat Seal measurements) with configurations for 3 replicates of a seal width: 1.0 inch; adhesion separation rate: 8 in / min; interruption time = 1,000 ms (1 s); seal pressure = 60 psi and peeling speed = 200 cm / min. (for hot grip) or 30 cm / min (for seal testing).
    [0061] The Hot Adhesion Initiation Temperature (HTIT) was defined as where the hot adhesion resistance of 1 N / 25 mm (0.225 lb / in) in cooling time 250 ms was reached. The Seal Initiation Temperature (SIT) was defined as when the Final Seal Resistance of 1.3 N / 25 mm (0.3 lb / in) was reached. The Hot Stick Initiation Temperature Range (HTR) was defined as the temperature window in which the Hot Stick Resistance of 0.225 lb / in or greater was achieved and was readily determined from the Force vs. Strength curve. Sealing temperature using a cooling time of 250 ms.
    [0062] Inventive samples (ie PITs) were prepared in a continuous loop loop process with liquid isobutane as a diluent. These pilot plant polymerizations were carried out in a 27-gallon reactor operating at about 590 psig and about 79.4 ° C (about 175 ° F). Inventive resins 1 to 20 were prepared using a metallocene mixture composed of an MTE-B + MTE-A in a weight ratio ranging from 2: 1 to 5: 1 = MTE-B: MTE-A. The metallocenes were fed to the reactor as a hydrocarbon solution simultaneously or in a single solution for the prescribed ratio through a pre-contact flask. The remaining inventive resins were prepared with a mixture of three metallocenes, two metallocenes type MTE-B and 1 metallocene type MTE-A. The three metallocenes were fed to the reactor in order to achieve a final weight ratio composition of 2: 1: 0.14 to 0.20 = MTE-B1 / MTE-A / MTE-B2.
    [0063] The polymer was removed from the reactor at a rate of about 22-25 pounds per hour, employing a total metallocene concentration ranging from 0.6 to 1.5 ppm in the reactor. The rate of polymer production was maintained by feeding ethylene at 22-32 lbs per hour and with the reactor operated to have a residence time of about 1.2 hours. The ethylene concentration varied from 10.7 to 13.9 mol% and the melting index and polymer density were controlled by the addition of hydrogen (0.4 to 5.97 milli lbs per h) and hexene (3.6 to 6.4 lbs per hour) to the reactor.
    [0064] The properties of the Inventive resins were compared with four Comparative samples. The basic properties of all these resins are shown in Table 1. All resin samples in Table 1 were formed in blown films of 1 mil thickness (25 microns) and the HTIT, HTR and SIT properties tested. These results are tabulated in Table 2. The thermal properties of the films were tested and these results are shown in Table 3. Comparative samples COMP 1, COMP 2 and COMP 4 are polyethylene based on metallocene catalyst which are commercially available from Chevron Phillips Chemical Company LP. COMP 3 is a polyethylene catalyzed by Ziegler-Natta. Table 1
    .

    nm - not measured Table 2

    Table 3

    nm - not measured
    [0065] In reference to Table 3, fog is the cloudy appearance of a material caused by light scattered from within the material or its surface. The mist of a material can be determined in accordance with ASTM D1003. TEDD is the total energy dart drop resistance (TEDD). TEDD measures the total failure energy absorbed by a film sample impacted by a dart falling under specified test conditions. Typically, a hemispherical head dart with a diameter of 3 8.1 mm (1.5 in.) Drops from 6 6 cm (26 in) and impacts a test sample. After passing through the test sample, the dart passes through a speed trap made of a pair of photoelectric sensors that measure the time it takes for the dart to travel a certain distance. The time it takes for the dart to pass the speed trap after passing the sample is referred to as the drop test time, while the time through the speed trap without a sample is called the free fall time. The energy absorbed by the sample is equated with the loss of kinetic energy of the dart and is determined using the formula: E (m / 2g) [d2 (l / ti2 + l / t22) + (g2 / 4) (ti2 - t22)] where E is the energy required to break the sample (J), m is the dart mass (kg), g is the gravitational constant (9.81 m / s2), d is the distance between the photoelectric sensors (m), ti is the free fall time (s), and t2 is the fall test time (s).
    [0066] The difference in the hot tack initiation temperature range can be attributable to the heterogeneous short chain branch distribution of the PIT samples. Figure 2 is a graph of the inventive HTIT (ie, PIT) and comparative films depending on the density of the resin while Figure 3 is a graph of HTR) of inventive (ie, PIT) and comparative films according to HTIT. The ATREF profiles of the samples in Table 1 are shown in Figures 4 and 5. The ATREF data suggest that the PIT samples contain a lower fusion, more branched population of polymer chains that result in the observed decrease in the initiation temperature of hot adhesion. . The results demonstrate that PITs of the type disclosed here form films having decreased hot adhesion initiation temperatures, but maintaining seal strengths comparable to films formed from conventional polyethylene resins.
    [0067] The following listed modalities are provided as non-limiting examples.
    [0068] A first embodiment which is a polymer composition comprising an ethylene alpha-olefin copolymer, wherein the polymer composition is characterized as having (a) a density in the range of greater than about 0.910 g / cm3 at about 0.930 g / cm3, as determined according to ASTM D1505; (b) a melting index in the range of greater than about 0.5 g / 10 min. at about 3 g / 10 min., as determined according to ASTM D1238, Condition 190 ° C / 2.16 kg; (c) a molecular weight distribution of about 3.4 to about 12, as determined by gel permeation chromatography; (d) a weight average molecular weight greater than about 85 kg / mol to about 160 kg / mol, as determined by gel permeation chromatography; and (e) average molecular weight z greater than about 210 kg / mol to about 500 kg / mol, as determined by gel permeation chromatography.
    [0069] A second embodiment which is the polymer composition of the first embodiment having a numerical average molecular weight of about 7 kg / mol to about 50 kg / mol.
    [0070] A third embodiment which is the polymer composition of any of the first to second embodiments having a high charge melt index of about 10 g / 10 min. at about 27 g / 10min.
    [0071] A fourth embodiment which is the polymer composition of any of the first to third embodiments having a high charge to melt ratio ratio of about 16 to about 30.
    [0072] A fifth embodiment which is the polymer composition of any one of the first to the fourth embodiment having a zero shear viscosity of about 3000 Pa.s to about 25000 Pa.s.
    [0073] A sixth embodiment which is the polymer composition of any one of the first to fifth embodiments having a CY-a of about 0.400 to about 0.600.
    [0074] A seventh modality that is a film formed from the polymer compositions of any one of the first to the sixth modality.
    [0075] An eighth modality that is the film of the seventh modality having a resistance to the drop of dart ranging from about 500 g / thousand to about 2000 g / thousand.
    [0076] A ninth modality that is the film of any of the seventh to eighth modality having an Elmendorf rupture resistance in the machine direction of about 70 g / mil to about 300 g / mil.
    [0077] A tenth modality that is the film of any of the seventh to ninth modality having a resistance to Elmendorf rupture in the transversal direction of about 250 g / mil to about 650 g / mil.
    [0078] An eleventh modality which is the film of any one of the seventh to eleventh modality having a seal initiation temperature of about 85 ° C to about 105 ° C.
    [0079] A twelfth embodiment which is a manufactured film article comprising a polymer composition comprising an alpha-olefin ethylene copolymer, wherein the polymer composition is characterized as having (a) a density in the range of greater than about from 0.910 g / cm3 to about 0.930 g / cm3, as determined according to ASTM D1505 (b) a melt index in the range of greater than about 0.5 g / 10 min. at about 3 g / 10 min. as determined according to ASTM D1238, Condition 190 ° C / 2.16 kg (c) a molecular weight distribution of about 3.4 to about 12, as determined by gel permeation chromatography; (d) a weight average molecular weight greater than about 85 kg / mol to about 160 kg / mol, as determined by gel permeation chromatography; and (e) average molecular weight z greater than about 210 kg / mol to about 500 kg / mol, as determined by gel permeation chromatography; so that the film article made from the polymer composition is characterized as having a hot tack initiation temperature of less than about 96 ° C, as determined by ASTM F1921-98, method A.
    [0080] A thirteenth modality which is the film manufactured from the twelfth modality in which the polymer composition has a numerical average molecular weight of about 7 kg / mol to about 50 kg / mol.
    [0081] A fourteenth modality which is the film manufactured from any one of the twelfth to the thirteenth modality in which the polymer composition has a high charge melting index of about 10 g / 10 min. at about 27 g / 10min.
    [0082] A fifteenth modality that is the film manufactured from any one of the twelfth to the fourteenth modality in which the polymer composition has to have a ratio of high melt index to melt index of about 16 to about of 30.
    [0083] A sixteenth modality which is the film manufactured from any one of the twelfth to the fifteenth modality in which the polymer composition has a zero shear viscosity of about 3000 Pa.s to about 25000 Pa.s.
    [0084] A seventeenth modality which is the film manufactured from any one of the twelfth to the sixteenth modality in which the polymer composition has a CY-a of about 0.400 to about 0.600.
    [0085] An eighteenth embodiment which is a manufactured film article comprising a polymer composition comprising an ethylene alpha-olefin copolymer, wherein the polymer composition is characterized as having (a) a density in the range of greater than about from 0.910 g / cm3 to about 0.930 g / cm3, as determined according to ASTM D1505 (b) a melt index in the range of greater than about 0.5 g / 10 min to about 3 g / 10 min, as determined by ASTM D1238, Condition 190 ° C / 2.16 kg (c) a molecular weight distribution of about 3.4 to about 12, as determined by gel permeation chromatography; (d) a weight average molecular weight greater than about 85 kg / mol to about 160 kg / mol, as determined by gel permeation chromatography; and (e) an average molecular weight z greater than about 210 kg / mol to about 500 kg / mol, as determined by gel permeation chromatography so that the film article made from the polymer composition is characterized as having: (i) a hot tack initiation temperature of less than about 96 ° C, as determined by ASTM F1921-98, method A; and (ii) a hot tack initiation temperature range greater than about 20 ° C, as determined by ASTM F1921-95, method A.
    [0086] A nineteenth modality which is the film of the eighteenth modality having a resistance to the drop of dart ranging from about 500 g / thousand to about 2000 g / thousand.
    [0087] A twentieth modality which is a method comprising forming the film of any one from the eighteenth to the nineteenth modality in a package, placing an item in the package, and heat sealing the package to include the item placed in it.
    [0088] While various types of disclosure are shown and described, modifications of them can be prepared by a specialist in the technique without departing from the spirit and teachings of the disclosure. The modalities described here are exemplary only, and are not intended to be a limiting factor. Many variations and modifications of the material disclosed here are possible and are within the scope of the disclosure. Where ranges or numerical limitations are expressly stated, those ranges or limitations must be understood to include iterative ranges or limitations of similar magnitudes covered in the ranges or limitations expressly established (for example, from about 1 to about 10 includes, 2, 3, 4, etc .; greater than 0.10 includes 0.11, 0.12, 0.13, etc.). For example, whenever a numerical range with a lower limit, RL, and an upper limit, Ru, is disclosed, any number falling within the range is also specifically disclosed. In particular, the following numbers within the range are specifically disclosed: R = RL + k * (R0-RL), where k is a variable ranging from 1 percent to 100 percent with an increase of 1 percent, that is , k is 1 percent, 2 percent, 3 percent, 4 percent, 5 percent,. . . , 50 percent, 51 percent, 52 percent,. . . , 95 percent, 96 percent, 97 percent, 98 percent, 99 percent, or 100 percent. In addition, any numerical range defined by two R numbers as defined above is also specifically disclosed. The use of the term "optionally" in relation to any element of a claim is intended to mean that the element is necessary, or alternatively, is not necessary. Both alternatives are intended to be within the scope of the claim. The use of broader terms, as understood, includes, having, etc. should be understood to provide support for narrower terms such as consisting of, consisting essentially of, composed substantially of, etc.
    [0089] In this sense, the scope of protection is not limited by the description stated above, but is only limited by the claims that follow, this scope including all equivalents of the subject matter of the claims. Each and all claims are incorporated into the specification as an embodiment of the present invention. Thus, the claims are an additional description and are an addition to the embodiments of the present invention. The discussion of a reference here is not a confession that is prior art to the present disclosure, especially any reference that may have a publication date after the priority date of this request. The disclosures of all patents, patent applications, and publications cited here are incorporated by reference, as they provide examples, processes, or other details complementary to those set forth here.
    权利要求:
    Claims (16)
    [0001]
    1. A polymer composition comprising an ethylene alpha-olefin copolymer characterized by having: (a) a density in the range greater than 0.910 g / cm3 to 0.930 g / cm3, as determined according to ASTM D1505; (b) a melt index in the range greater than 0.5 g / 10 min to 2.5 g / 10 min, as determined in accordance with ASTM D1238, Condition 190 ° C / 2.16 kg; (c) a molecular weight distribution of 3.4 to 12, as determined by gel permeation chromatography; (d) a weight average molecular weight greater than 85 kg / mol to 160 kg / mol, as determined by gel permeation chromatography; (e) an average molecular weight z greater than 210 kg / mol to 500 kg / mol, as determined by gel permeation chromatography; and a CY-a of 0.400 to 0.680, when the dynamic complex viscosity versus the frequency sweep are adjusted for the Carreau-Yasuda equation with a value of n = 0.1818.
    [0002]
    Polymer composition according to claim 1, characterized in that it has a high charge melting index of 10 g / 10 min at 27 g / 10 min, or has a high charge melting ratio of 16 to 30 .
    [0003]
    Polymer composition according to claim 1, characterized in that it has a CY-a value of 0.400 to 0.600.
    [0004]
    Film characterized by being formed from the polymer composition as defined in claim 1.
    [0005]
    5. Film according to claim 4, characterized by having a dart drop resistance ranging from 20,833 g / mm to 83,333 g / mm (500 g / mil to 2000 g / mil).
    [0006]
    6. Film according to claim 4, characterized by having an Elmendorf tear strength in the machine direction of 2,917 g / mm (70 g / mil) to 12,500 g / mm (300 g / mil), or having a resistance at Elmendorf rupture in the transverse direction from 10,417 g / mm (250 g / mil) to 27,083 g / mm (650 g / mil).
    [0007]
    Film according to claim 4, characterized in that it has a seal initiation temperature of 85 ° C to 105 ° C.
    [0008]
    8. Manufactured film article characterized by comprising a polymer composition, as defined in claim 1, and having a hot adhesion initiation temperature of less than 96 ° C, as determined according to ASTM F1921-98, method A.
    [0009]
    9. Film article according to claim 8, characterized by the fact that the polymer composition has a numerical average molecular weight of 7 kg / mol to 50 kg / mol.
    [0010]
    10. Film article according to claim 8, characterized by the fact that the polymer composition has a high charge melting index of 10 g / 10min to 27 g / 10min.
    [0011]
    11. Film article according to claim 8, characterized by the fact that the polymer composition has a high charge to melt ratio ratio of 16 to 30.
    [0012]
    12. Film article according to claim 8, characterized in that the polymer composition has a zero shear viscosity from 3000 Pa.s to 25000 Pa.s.
    [0013]
    13. Film article according to claim 8, characterized by the fact that the polymer composition has a CY-a of 0.400 to 0.600.
    [0014]
    14. Film article according to claim 8, characterized in that it also has a hot adhesion initiation temperature greater than 20 ° C, as determined by ASTM F1921-95, method A.
    [0015]
    15. Film article according to claim 14, characterized by having a dart drop resistance ranging from 20,833 g / mm (500 g / mil) to 83,333 g / mm (2000 g / mil).
    [0016]
    16. Method characterized by comprising forming the film article, as defined in claim 15, in a package, placing an item in the package and heat-sealing the package to wrap the item placed in it.
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    公开号 | 公开日
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    法律状态:
    2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-12-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-07-07| B09A| Decision: intention to grant|
    2020-08-18| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 06/03/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US13/794,070|US9181369B2|2013-03-11|2013-03-11|Polymer films having improved heat sealing properties|
    US13/794,070|2013-03-11|
    PCT/US2014/021132|WO2014164192A1|2013-03-11|2014-03-06|Polymer films having improved heat sealing properties|
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