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    • 专利摘要:
    POLYMERIC RESINS WITH IMPROVED PROCESSABILITY AND FUSION FRACTURE CHARACTERISTICS A metallocene-catalyzed polymer comprising (i) a higher molecular weight component and (ii) a lower molecular weight component where the polymer has a polydispersity index of about 10 to about 26; a zero shear viscosity of about 5x105 Pa.s to about 2x1014 Pa.s and a soft to matte critical transition stress of about 20kPa to about 85 kPa at a shear rate of about 1.5 s-1 at about 17 s- 1. A dual metallocene-catalyzed polyethylene comprising (i) a higher molecular weight component and (ii) a lower molecular weight component where the polymer has a polydispersity index of about 10 to about of 26; a zero shear viscosity of about 5x105 Pa.s to about 2x1014 Pa.s and a soft to matte transition tension of about 20kPa to about 85 kPa at a shear rate of about 1.5 s-1 to about of 17 s-1.
    公开号:BR112015020593B1
    申请号:R112015020593-3
    申请日:2014-02-25
    公开日:2020-06-30
    发明作者:Yongwoo Inn；Qing Yang
    申请人:Chevron Phillips Chemical Company Lp.；
    IPC主号:
    专利说明:

    [0001] [1] This disclosure relates in general to polymeric compositions and methods of producing and using them. More specifically, the present disclosure relates to polymeric compositions having improved melt processability and fracture characteristics. FIELD
    [0002] [2] Polyolefins are plastic materials useful for the manufacture of a wide variety of valuable products, due to the combination of characteristics such as rigidity, ductility, barrier properties, temperature resistance, optical properties, availability and low cost. Particularly, polyethylene (PE) is one of the largest volume polymers consumed in the world. It is a versatile polymer that offers high performance compared to other polymers and alternative materials such as glass or metal.
    [0003] [3] There is a latent need for improved polymeric compositions showing desired processing characteristics. BRIEF SUMMARY
    [0004] [4] A metallocene-catalyzed polymer is disclosed here comprising (i) a higher higher molecular weight component and (ii) a lower lower molecular weight component in which the polymer has a polydispersity index of about 10 about 26; a zero shear viscosity of about 5x10 5 Pa.s to about 2 x10 14 Pa.s and a critical soft to matte transition stress of about 20 kPa to about 85 kPa at a shear rate of 1.5 s -1 to 17 s -1 .
    [0005] [5] A dual metallocene catalyzed polyethylene comprising (i) a higher higher molecular weight component and (ii) a lower lower molecular weight component, where the polymer has a polydispersity index of about 10 to about 26; a zero shear viscosity of about 5x10 5 Pa.s to about 2x10 14 Pa.s and a soft to matte transition tension of about 20 kPa to about 85 kPa at a shear rate of about 1.5 s -1 to 17 s -1 . BRIEF DESCRIPTION OF THE DRAWINGS
    [0006] [6] Figure 1 depicts the structures of the compounds used in the preparation of the samples in Example 1.
    [0007] [7] Figure 2 is a molecular weight distribution profile of the samples in example 1.
    [0008] [8] Figure 3 is a graph of viscosity versus frequency for the samples in example 1. DETAILED DESCRIPTION
    [0009] [9] Unpublished polymers and methods for their manufacture and use are disclosed here. Here, the polymer refers both to a collected material and the product of a polymerization reaction (for example, a reactor or virgin resin) and to 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 herein to produce a polymer of the type disclosed here.
    [0010] [10] In one embodiment, polymers of the type disclosed here are characterized as polymers catalyzed by metallocene having improved processability and designated as POL-IPs. Additional features of POL-IPs are disclosed here.
    [0011] [11] In one embodiment, a POL-IP of the type described here can be prepared by any methodology that is compatible, for example, by using one or more catalyst systems, in one or more reactors, in solution, in paste, or in the gas phase, and / or by varying the concentration of the monomer in the polymerization reaction, and / or by changing one / all of the materials or parameters involved in the production of POL-IPs, as will be described in more detail here.
    [0012] [12] The POL-IP of the present disclosure can be produced using different types of polymerization reactors. As used herein, "polymerization reactors" 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, but are not limited to, those that can be referred to as reactors and / or batch reactors, paste, gas phase, solution, high pressure, tubular, autoclave or others. Gas phase reactors can comprise fluidized bed reactors or horizontal staged reactors. Slurry reactors can comprise horizontal and / or vertical circuits. High pressure reactors may comprise autoclave and / or tubular reactors. Reactor types can include batch and / or continuous processes. Continuous processes may use intermittent and / or continuous product discharge or transfer. Processes may also include direct partial or total recycling of unreacted monomer, unreacted comonomer, catalyst and / or cocatalysts, diluents and / or other materials from the polymerization process.
    [0013] [13] Polymerization reactor systems of the present disclosure may comprise one type of reactor in a system or multiple reactors of the same or different types operated in any suitable configuration. Production of polymers in multiple reactors can include several stages in at least two separate polymerization reactors interconnected by a transfer system making it possible to transfer polymers resulting from the first polymerization reactor to 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-stage or multiple-stage polymerization can occur in a single reactor, where conditions are changed so that a different polymerization reaction occurs.
    [0014] [14] The desired polymerization conditions in one of the reactors can be the same or different from the operating conditions in any other reactors involved in the general polymer production process in the present disclosure. Multiple reactor systems may include any combinations including, but not limited to, multiple circuit reactors, multiple gas phase reactors, a combination of circuit and gas phase reactors, multiple high pressure reactors or a combination of high pressure reactors with circuit and / or gaseous. The multiple reactors can be operated in series or in parallel. In one embodiment, any arrangement and / or combination of reactors can be employed to produce the polymer of the present disclosure.
    [0015] [15] According to one embodiment, the polymerization reactor system can include at least one slurry loop reactor. Such reactors can include vertical or horizontal circuits. Monomers, diluents, catalyst systems and optionally any comonomers can be continuously fed into a slurry reactor, where polymerization takes place. Generally, continuous processes may include the continuous introduction of a monomer, a catalyst and / or a diluent into a polymerization reactor and the continuous removal of that reactor from a suspension containing polymeric particles and the diluent. Effluents from the reactor can be vaporized to remove liquids that comprise the solid polymer, monomer and / or comonomer diluent. Various technologies can be used for this separation step, including, but not limited to, vaporization which may include any combination of heat addition and pressure reduction; separation by cyclonic action in a cyclone or a hydrocyclone; centrifugation separation; or another appropriate method of separation.
    [0016] [16] Typical paste polymerization processes (also known as particulate processes) are described 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 these is incorporated as a reference in its entirety.
    [0017] [17] Appropriate diluents used in paste polymerization include, but are not limited to, the monomer being polymerized and hydrocarbons that are liquid under the reaction conditions. Examples of such suitable diluents include, but are not limited to, hydrocarbons such as propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane and n-hexane. Some polymeric circuit reactions can occur in various conditions where diluents are not being used. As an example is the polymerization of the propylene monomer as described in US Patent 5,455,314, which is incorporated by reference in its entirety.
    [0018] [18] According to another embodiment, the polymerization reactor can comprise at least one gas phase reactor. Such systems can employ a continuous recycling stream containing one or more monomers continuously circulated in a fluidized bed in the presence of a catalyst under polymerization conditions. A recycling stream can be removed from the fluidized bed and recycled back to the reactor. Simultaneously, polymeric products can be removed from the reactor and new or fresh monomers can be added to replace the polymerized monomer. Such gas-phase reactors can comprise a process for multi-stage gas phase polymerization of defines, in which the defines are polymerized in the gas phase in at least two independent zones of gas phase polymerization, while feeding a polymer containing catalysts formed in a first polymerization zone for a second polymerization zone. A type of gas phase reactor is described in US Patents 4,588,790, 5,352,749 and 5,436,304, each of which is incorporated herein by reference in its entirety.
    [0019] [19] According to yet another modality, a high pressure polymerization reactor can include a tubular reactor or an autoclave reactor. Tubular reactors can have several zones where fresh monomers, initiators or catalysts are added. Monomers can be entrained in an inert gas stream and introduced into a reactor zone. Primers, catalysts and / or catalyst components can be entrained in a gaseous stream and introduced into other areas of the reactor. Gaseous streams can be intermixed for polymerization. Heat and pressure can be appropriately employed to obtain the optimum polymerization reaction conditions.
    [0020] [20] According to yet another modality, the polymerization reactor can comprise a solution polymerization reactor in which the monomer comes into contact with the catalyst composition by proper stirring or other means. A carrier comprising an excess organic diluent or monomer can be used. If desired, the monomer can be placed in contact, in the vapor phase, with the product of the catalytic reaction 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 better temperature control and to maintain a uniform polymerization mixture through the polymerization zone. Suitable means are used to dissipate the exothermic heat from polymerization.
    [0021] [21] 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 feedstock recovery system. polymer. Reactor systems suitable for the present invention may further comprise systems for purification of raw material, storage and preparation of catalyst, extrusion, reactor cooling, polymer recovery, fractionation, recycling, storage, discharge, laboratory analysis and process control.
    [0022] [22] Conditions that are controlled for the polymerization efficiency and to provide the properties of the polymers include, among others, temperature, pressure, type and quantity of catalyst or cocatalyst and the concentrations of various reagents. The polymerization temperature can affect the productivity of the catalyst, the molecular weight of the polymer and the molecular weight distribution. Suitable polymerization temperatures can be any temperature below the depolymerization temperature, according to the Gibbs Free Energy Equation. Typically, this includes from about 60 ° C to about 280 ° C, for example, and / or from about 70 ° C to about 110 ° C, depending on the type of polymerization reactor and / or polymerization process.
    [0023] [23] Appropriate pressures also vary according to the reactor and the 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 to 500 psig. High pressure polymerizations in tubular reactors or autoclaves generally stay at around 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 on the pressure / temperature diagram (supercritical phase) can offer advantages.
    [0024] [24] The concentration of several reagents can be controlled to produce polymers with certain mechanical and physical properties. The proposed final product that will be formed by the polymer and the method of forming that product can be changed to determine the final characteristics of the product. Mechanical properties include, but are not limited to, tensile strength, bending modulus, impact resistance, deformation, stress and hardness relaxation 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 branches, long chain branches and rheological measurements.
    [0025] [25] Concentrations of monomer, comonomer, hydrogen, cocatalyst, modifiers and electron donors are generally important in the production of specific polymeric properties. Comonomers can be used to control product density. 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 impact reactions and / or otherwise affect the properties of the polymeric product. Modifiers can be used to control product properties and electron donors can affect stereoregularity.
    [0026] [26] In one embodiment, a method of preparing a POL-IP 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 herein. 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 the contact or reaction of the components of the mixtures, the nature of the active catalytic site or the fate of the cocatalyst, the catalyst, of any olefin monomer used to prepare a pre-contacted mixture or activator support, after combining these components. Therefore, the terms "catalyst composition", "catalyst mixture", "catalyst system" and the like, can include both heterogeneous and homogeneous compositions.
    [0027] [27] In one embodiment, a catalyst system suitable for the production of a POL-IP comprises at least one metallocene-containing compound. Here, the term "metallocene" describes a compound comprising at least one type fraction ɳ 3 to 5 ɳ -cicloalcadienil where ɳ fractions 3 to 5 ɳ - cicloalcadienil include cyclopentadienyl ligands, indenyl ligands, fluorenyl ligands , and the like, including partially unsaturated derivatives or substituted for them, or analogues of any of these. Possible substitutes for these binders include hydrogen, so the description "substituted derivatives thereof" in this disclosure comprises partially saturated binders such as tetrahydrodenyl, tetrahydrofluorenyl, octohydrofluorenyl, partially saturated indenyl, partially saturated fluorenyl, partially substituted fluorenyl, partially substituted fluorenyl saturated and the like.
    [0028] [28] In one embodiment, a catalyst system suitable for the preparation of POL-IP contains at least two compounds containing metallocene. 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; 5,555,592; 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 in US patent applications 20100190926 A1 and 20120059134, each of which is incorporated herein by reference in its entirety. Other processes for preparing metallocene compounds suitable for use in this disclosure have been described in references such as: Koppl, A. Alt, H. G. J. Mol. Catal. A. 2001, 165, 23; Kajigaeshi, S .; Kadowaki, T .; Nishida, A .; Fujisaki, S. The Chemical Society of Japan, 1986, 59, 97; Alt, H. G .; Jung, M .; Kehr, G. J. Organomet. Chem. 1998, 562, 153-181; and Alt, H. G .; Jung, M. J. Organomet. Chem. 1998, 568, 87-112; each of which is incorporated by reference herein in its entirety. The following treatises also describe such methods: Wailes, P. C .; Coutts, R. S. P .; Weigold, H. in Organometallic Chemistry of Titanium, Zirconium, and Hafnium, Academic; New York, 1974 .; Cardin, D. J .; Lappert, M. F .; and Raston, C. L .; Chemistry of Organo-Zirconium and -Hafnium Compounds; Halstead Press; New York, 1986. In one embodiment, POL-IP is prepared using a catalyst system containing two compounds containing metallocene that can be characterized as dual metallocene polymers or a dual metallocene resin. In one embodiment, said metallocene catalysts can be used to prepare bimodal or bimodal type resins disclosed here.
    [0029] [29] In one embodiment, the dual metallocene catalyst used to prepare POL-IP comprises an unbound metallocene, designated MTE-A. In one embodiment, MTE-A is a compound that can be characterized by one of two general formulas 1 or 2:
    [0030] [30] In one embodiment, the dual metallocene catalyst used for the preparation of POL-IP comprises a bonded metallocene compound designated here MTE-B. In one embodiment, MTE-B can be characterized by formulas 3 or 4:
    [0031] [31] POL-IP may contain additives. Examples of additives include, but are not limited to, antistatic agents, dyes, stabilizers, nucleators, surface modifiers, pigments, glidants, anti-blocks, tackiness agents, polymer processing aids and combinations thereof. Such additives can be used individually or in any combination and can come in contact with the polymer before, during or after the preparation of POL-IP as described here. Such additives can be added by any appropriate technique, for example, during the extrusion or composition step, such as during pelletizing or subsequent processing on an end-use article.
    [0032] [32] In one embodiment, POL-IP contains polyethylene. For example, POL-IP can comprise a polyethylene homopolymer. It should be understood that an inconsequential amount of comonomer may be present in the polymers disclosed herein and the polymer will still be considered a homopolymer. Here, an inconsequential amount of comonomer refers to an amount that does not substantially affect the properties of the polymer disclosed herein. For example, a comonomer may be present in an amount below 0.5% w / w, 0.1% w / w or 0.01% w / w based on the total weight of the polymer.
    [0033] [33] In an alternative embodiment, POL-IP comprises a polyethylene copolymer. Examples of suitable comonomers include, but are not limited to, unsaturated hydrocarbons having 3 to 20 carbons, 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. In some embodiments, POL-IP is a copolymer of ethylene and 1-hexene. The applicability of the aspects and characteristics disclosed here for polymers of linear defines other than ethylene (for example, propylene and 1-butylene) and copolymers of defines, is also contemplated.
    [0034] [34] A POL-IP of the type described here can be a multimodal resin. Here the "modality" of a polymeric resin refers to the shape of the molecular weight distribution curve, that is, the appearance of the graph of the polymer's weight fraction as a function of its molecular weight, as can be demonstrated, for example, by a gel permeation chromatography (GPC / SEC). The weight fraction of the polymer refers to the weight fraction of molecules of a given size. A polymer having a molecular weight distribution curve showing a single peak can be referred to as a unimodal polymer, a polymer with a curve showing two distinct peaks can be referred to as a bimodal or bimodal type polymer, and a polymer having a distribution curve showing three distinct peaks can be referred to as a trimodal polymer and etc. Polymers having molecular weight distribution curves having more than one peak can be collectively referred to as multimodal polymers or resins. It is recognized that, in some cases, a multimodal polymer may appear to have a single peak via, for example, GPC analysis, when in fact the polymer itself is multimodal. In such cases, the overlapping of peaks can obstruct the presence of other peaks and may imply unimodality, when in fact multimodality is a more adequate representation of the nature of the polymer or polymers.
    [0035] [35] In one embodiment, POL-IP is characterized as a bimodal type resin. Such a bimodal resin can have two peaks in a GPC profile, but it is different from conventional bimodal resins. A GPC of a POL-IP of the type described here may exhibit the following identifiable characteristics (i) a peak attributable to a higher molecular weight component (HMW) (ii) a peak attributable to a lower molecular weight component (LMW ) where the peak attributable to the HMW component and the LMW component are not separated by the baseline.
    [0036] [36] In one embodiment, the LMW component is present in the POL-IP in an amount ranging from about 70 weight percent (% w / w) to about 97% w / w, alternatively about 80% w / w p to about 90% w / w. In another embodiment, the HMW component is present in POL-IP in amounts of about 3% w / w to about 30% w / w, alternatively from about 5% w / w to about 25% w / w or alternatively from about 5% w / w to about 20% w / w. The individual components of the polymer composition can be obtained by deconvolution of a polymer GPC (e.g., POL-IP) as described in US patent publication 20070298508 incorporated herein by reference in its entirety.
    [0037] [37] In one embodiment, POL-IP has a weight average molecular weight (Mw) of about 260 kg / mol to about 360 kg / mol, alternatively from about 280 kg / mol to about 350 kg / mol or alternatively about 290 kg / mol to about 340 kg / mol. In one embodiment, POL-IP has a numerical average molecular weight (Mn) of about 12 kg / mol to about 26 kg / mol, alternatively from about 13 kg / mol to about 25 kg / mol or alternatively about 14 kg / mol to about 24 kg / mol. In one embodiment, POL-IP has an average molecular weight z of about 1500 kg / mol to about 2500 kg / mol, alternatively from about 1550 kg / mol to about 2400 kg / mol or alternatively from about 1600 kg / mol up to about 2350 kg / mol. The average molecular weight describes the molecular weight distribution of a polymeric composition and is calculated according to equation 1:
    [0038] [38] POL-IP can further be characterized by a molecular weight distribution (MWD) of the entire polymer from about 10 to about 26, alternatively from about 11 to about 25 or from about 12 to about 24. POL-IP can also be characterized by a MWD for the HMW component of about 1.3 to about 2, alternatively about 1, 4 to about 1, 9, or alternatively about 1, 5 up to about 1, 9. POL-IP can still be characterized by a MWD of the LMW component between about 4 to about 9, alternatively between about 4, 5 to about 9 or from about 5 to about 8 MWD refers to the average weight ratio Mw to Mn, which can also be referred to as the polydispersity index (PDI) or more commonly polydispersity.
    [0039] [39] POL-IP can further be characterized as having an M z / M w of about 5 to about 9, alternatively from about 5.5 to about 8.5, or from about 5.7 to about 8.
    [0040] [40] POL-IP can be characterized by the degree of branching present in its individual components and / or in the composition as a whole. Short chain branching (SCB) is known for its effects on polymeric properties such as rigidity, tension properties, heat resistance, hardness, permeation resistance, shrinkage, deformation resistance, transparency, stress crack resistance, flexibility, strength impact and solid state properties of semicrystalline polymers such as polyethylene. In one embodiment, a polymer of the type described here (ie, POL-IP) and further characterized by a reverse branch distribution of the comonomers or a reverse short chain branch distribution (SCBD) resulting in a SCB that occurs primarily in the component HMW resulting from the polymer. For example, between about 50 percent (%) to about 85% of the SCB can be located within the HMW component of POL-IP, alternatively from about 60% to about 80% or about 65% to about 80%. Here, SCBD refers to the number of SCBs per 1000 carbon atoms, in each molecular weight through the MWD profile of a polymer.
    [0041] [41] In one embodiment, a polymer of the type demonstrated here (ie POL-IP) is characterized by a short chain branch content of about 0.5 to about 3.5 short chain branches per 1000 total carbon atoms, alternatively from about 0.5 to about 3.0, or from about 1 to about 3 or about 1 to about 2.5.
    [0042] [42] Long chain branches (SCB) have an effect on the rheology of a polymer. A POL-IP can contain from about 0.002 to about 0.2 long chain branching (LCB) per 1,000 total carbon atoms, alternatively from about 0.001 to about 0.1 LCB per 1000 total carbon atoms or alternatively about 0.003 and 0.3 LCB per 1000 total carbon atoms; where the LCB content is determined by the Janzen-Colby model found in J. Janzen and RH Colby, J. of Molecular Structure, 485, 569 (1999) .
    [0043] [43] The POL-IP can be characterized as having a density of about 0.945 g / cm 3 to about 0. 955 g / cm3, alternatively from about 0.948 g / cm 3 to about 0.955 g / cm 3 or alternatively from about 0.950 g / cm 3 to about 0.955 g / cm 3 as determined according to ASTM D 1505.
    [0044] [44] POL-IP can be characterized by having a high charge melting index (HLMI) of about 5 g / 10 min to about 12 g / 10 min, alternatively about 5 g / 10 min and about from 10 g / 10 min, alternatively from about 6 g / 10 min to about 10 g / 10 min, or alternatively from about 6 g / 10 min to about 9 g / 10 min. HLMI refers to the amount of polymer that can be forced through a 0.0825 inch diameter extrusion rheometer orifice when subjected to a force of 21.6 kilograms in ten minutes at 190 ° C, as determined according to ASTM D 1238.
    [0045] [45] In one embodiment, a POL-IP of the type described here has a zero shear viscosity ( E o ), in the range of about 5x10 5 Pa-s to about 2x10 14 Pa-s, alternatively about 5x10 5 Pa-s and 1.5x10 14 Pa-s, alternatively from about 6x10 5 Pa-s to about 1.5x10 14 Pa-s, or alternatively from about 6x10 5 Pa-s to about 1.3x10 14 Pa-s as determined according to the Carreau-Yasuda (CY) model which is represented by equation (4) when n = 0, 1818:
    [0046] [46] To facilitate model adaptation, the power law constant n is maintained as a constant value. Details of the significance and interpretation of the CY model and derived parameters can be found at: CA Hieber and HH Chiang, Rheol . Acta, 28, 321 (1989); CA Hieber and HH Chiang, Polym. Eng. Sci., 32, 931 (1992); and RB Bird, RC Armstrong and O. Hasseger, Dynamics of Polymeric Liquids, Volume 1, Fluid Mechanics , 2nd Edition, John Wiley & Sons (1987), each of which is incorporated by reference in its entirety.
    [0047] [47] 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 the materials. In addition, for polymeric fusions, viscosity at zero shear is often a useful indicator of processing attributes such as the melt strength in polymeric fusions for polymeric processes. For example, the higher the zero shear viscosity, the better the melt strength.
    [0048] [48] In one embodiment, POL-IP has an "a" value of about 0.03 to about 0.4, alternatively from about 0.033 to about 0.39, alternatively from about 0.033 to about 0.385 or from about 0.035 to about 0.38 where complex dynamic viscosity versus frequency sweep are adjusted for the Carreau-Yasuda equation with a value of n = 0.1818.
    [0049] [49] In one embodiment, the POL-IP has a "tau eta" (Tç) value of about 7 seconds (s) at about 2x10 5 s, alternatively from about 8 s to about 1.8x10 5 s, alternatively from about 8 s to about 1, 5x10 5 s, or from about 9 s to about 1x10 5 s in which the complex dynamic viscosity versus the frequency sweep are adjusted for the Carreau-Yasuda equation with a value of n = 0 , 1818.
    [0050] [50] In one embodiment, a POL-IP prepared as described herein can demonstrate reduced melt fractures during the formation and processing of the molten polymer when compared to a typical dual metallocene catalyzed polymer. The type, extent and conditions under which the molten polymer undergoes melt fracture may vary depending on the polymer's microstructure. In one embodiment, a POL-IP of the type described here demonstrates a reduced tendency to melt fractures as determined by measuring the shear stress as a function of the shear rate using capillary rheometry.
    [0051] [51] Capillary rheometry is a technique whereby a sample is extruded through a mold with defined dimensions and the shear pressure through the mold is recorded at defined volumetric flow rates. In one embodiment, a POL-IP is the material of a capillary extrusion experiment to characterize the polymer's melting fracture behavior. The capillary extrusion experiment can be performed with any suitable methodology. For example, capillary extrusion experiments can be carried out at 190 ° C, using a double-diameter capillary rheometer (Rosand RH-7, Malvern) operated in constant speed mode. A capillary mold 1 mm in diameter and 16 mm long and an outlet mold 1 mm in diameter can be used. The entry angle for the molds can be 180 °, and the rate of contraction of the reservoir barrel for the tool can be about 15. A step shear rate test can be performed for a given sample to obtain the rate apparent wall shear stress ( Ẏ A ) and the apparent wall shear stress (σ A ) according to equation 5:
    [0052] [52] In one embodiment, POL-IP demonstrates a smooth to matte transition that occurs under critical stress of about 20kPa to about 85kPa, alternatively from about 30kPa to about 80kPa or alternatively from about 35kPa to about 70 kPa. Critical stress refers to the critical shear stresses of the wall that serve as a trigger for the initiation of distortion of the particular extrudate or melting fracture. The soft to matte transition can also be referred to as a surface melting fracture (SMF) or shark skin melting fracture (SSMF). The start of the soft to matte transition reaction is a polymer instability that originates at the exit of a mold during the extrusion of a molten polymer (eg melting) through the mold. The transition from soft to matte may be attributable to the acceleration (high stretch rate) of the melt as soon as it leaves the mold. Without wishing to be bound by theory, a hypothesis is developed that the molten material leaving the mold in the vicinity of the wall experiences a large, rapid tensile deformation while the speed field adjusts from the non-slip boundary condition to a free surface condition . The great stresses on the free surfaces cause periodic cracks that result in periodic distortions of small amplitude, known as shark skin, which is a visible defect in the surface present in the product being produced by the matrix (for example, tube). Critical stress is related to the beginning of the smooth to matte transition. In one embodiment, a POL-IP can reveal a transition from soft to matt that occurs at a critical shear rate of about 1.5 s -1 to about 17 s -1 , alternatively about 1.2 s - 1 to about 16, 5 s -1 alternatively from about 1.8 s -1 to about 16, 5 s -1 , alternatively from about 1.4 s -1 to about 16 s -1 or alternatively from about 1.6 s -1 to about 18 s -1 . Here, the shear rate refers to the extrusion speed that serves as a trigger for the initiation of a particular extrusion distortion or melting fracture.
    [0053] [53] In one embodiment, POL-IP has a Slipstick fracture magnitude (SSF) of about 200 psi to about 120 psi, alternatively from about 217 psi to about 1100 psi, alternatively from about 210 psi to about 1100 psi or about 220 psi to about 1000 psi. SSF is believed to occur when the shear stress on the mold wall exceeds the critical stress. When this occurs, the melt is pushed like a pin, relieving the pressure behind it and allowing the next oriented chain segments to retreat in some way. As soon as the pressure is released, the rate of movement of the polymer decreases and this re-establishes the non-slip limit condition. During SSF the internal pressure inside the mold fluctuates and the polymer outlet is fickle. The magnitude of the SSF pressure oscillation is recorded and correlated to the beginning of fusion fractures.
    [0054] [54] A POL-IP can demonstrate improved processability as indicated by the value N_100, which is the sloped viscosity curve at a frequency of 100 rad / s. The N_100 is generally a useful indicator of output in polymeric processes. For example, a POL-IP may have an N_100 value of about 0.2 to about 0.5, alternatively from about 0.23 to about 0.49, or alternatively from about 0.25 to about 0.47.
    [0055] [55] Further processing improvements may include a decrease in head pressure. Viscosity at 100 rad / s is a useful indicator that correlates with the extrusion pressure in polymeric processes. For example, a POL-IP may have a viscosity at 100 rad / s with values of about 2x10 3 Pa.s to about 2, 4x10 3 Pa.s, alternatively about 1, 9x10 3 Pa.sa to about 2 , 3x10 3 Pa.s, or about 1, 8x10 3 Pa.s to about 2, 2x10 3 Pa.s.
    [0056] [56] In one embodiment, POL-IP is contacted with one or more polymer processing aids (PPAs) to form a POL-IP or POL-IPC composition. A PPA works to improve the processing characteristics of the polymer and to eliminate surface imperfections that may occur during processing. Any suitable PPA can be joined with POL-IP to form a composition suitable for use in that description. Examples of PPAs suitable for use with POL-IP include, but are not limited to, fluorelastomers, polyethylene glycol, lower molecular weight polyethylene waxes and combinations thereof. In one respect, PPA is a fluorelastomer. POL-IPCs may have processing and / or melting fracture characteristics that are similar to those previously described here for POL-IP. In some embodiments, the processing and / or melting fracture characteristics of POL-IPCs are improved compared to those in POL-IP. In one embodiment, a POL-IP of the type described here is characterized by the ability to form a compound with a PPA (for example, fluoroelastomer) (ie, to form a POL-IPC) that has characteristics of processing and / or melting fracture improved.
    [0057] [57] As described here, POL-IPs can be formed into a variety of articles, including, but not limited to, household packaging, utensils, film products, drums, fuel tanks, pipes, geomembranes and coatings. In one aspect, the POL-IP of this description is manufactured in a pipeline by a process of plastic modeling such as extrusion.
    [0058] [58] Pipeline extrusion, in its simplest explanation, is performed by melting, transforming polyethylene pellets into a particular shape (usually an annular shape), and solidifying that shape during a cooling process. There are several steps for pipe extrusion, as provided below. The raw material for the polymer can be a pre-pigmented polyethylene resin or it can be a mixture of a polyethylene in its natural color and a colored concentrate (here referred to as "salt and pepper mixture"). In North America, the most commonly used raw material is the "salt and pepper mix". In Europe and other areas of the world, the most commonly used raw material is pre-pigmented polyethylene resin. The raw material is strictly controlled to obtain a properly finished product (tube) and final consumer specifications.
    [0059] [59] The raw material is then fed into an extruder. The most common extrusion system for pipe production is a single screw extruder. The purpose of this extruder is to melt, transport and homogenize the polyethylene pellets. Extrusion temperatures generally remain from about 178 ° C to about 250 ° C depending on the design of the extruder thread and the fluid properties of the polyethylene.
    [0060] [60] The molten polymer is then passed through a mold. The mold distributes the melt of homogeneous polyethylene polymer around a solid mandrel, which molds the polyethylene into an annular shape. Adjustments can be made at the exit of the mold to try to compensate for the polymer decay until the end of the process. In order for the tube to comply with the appropriate dimensional parameters, the tube is then dimensioned. There are two methods for sizing: vacuum and pressure. Both employ different techniques and equipment.
    [0061] [61] The tube is then cooled and solidified to the desired dimensions. Cooling is achieved by using several water tanks where the outer tube is submerged or sprayed with water in the outer tube. The tube is cooled from the outer to the inner surface. The inner wall and inner surfaces of the tube can remain hot for a long time, since polyethylene is a weak conductor of heat. Finally, the tube is printed and threaded or cut to length. EXAMPLES
    [0062] [62] Molecular weight and molecular weight distribution were obtained using a PL-GPC 220 system (Polymer Labs, an Agilent company) equipped with an IR4 detector (Polymer Char, Spain) and three Styragel HMW-6E GPC columns (Waters , MA) operating at 145 ° C. The flow rate of the mobile phase 1, 2, 4-trichlorobenzene (TCB) containing 0.5 g / L of 2,6-di-t-butyl-4-methylphenol (BHT) was obtained at 1 ml / min and the concentration of the polymeric solutions was generally maintained in the range of 1.0-1.5 mg / mL, depending on the molecular weight. Sample preparation was carried out at 150 ° C for 4 h with occasional, gentle shaking before the solutions were transferred to sample vials for injection. The integral calibration method was used for the deduction of molecular weights and the distribution of molecular weights using a HDPE polyethylene resin from Chevron Philips Chemicals Company, MARLEX BHB5003, as a comprehensive standard. The comprehensive table of the comprehensive standard was predetermined in a separate experiment with SEC-MALS.
    [0063] [63] For dynamic frequency scan measurement, PE pellet samples (ie POL-IPs) were molded by compression at 182 ° C for a total of 3 minutes. The samples were allowed to melt under relatively low pressure for 1 minute, and then at a high molding pressure for an additional 2 minutes. The molded samples were quenched in a low temperature press (room temperature), then discs with a diameter of 25.4 mm were stamped from the molded plates for measurement on a rotary rheometer. Measurements were performed on parallel plates of 25 mm in diameter at 190 ° C using a tension controlled rheometer equipped with a pneumatic rolling system (Physica MCR-500, Anton Paar). The rheometer test chamber was purged with nitrogen to minimize oxidative degradation. After thermal equilibrium, the samples were compressed between 1.6 mm thick plates, and the excess was trimmed. The dynamic frequency sweep test was performed with 1 ~ 10% voltage in the LVE regime at angular frequencies of about 0.0316 rad / s to 316 rad / s. Lower values of tension were used in samples of higher viscosity to avoid overloading the torque transformer and to remain within the limits of linear viscoelasticity of the sample. The instrument automatically reduces the voltage at high frequencies if necessary to avoid overloading the torque transducer. These obtained data were inserted in the Carreau-Yasuda equation to determine the zero shear viscosity ( η 0 ), the relaxation time ( ℸ ) and a measure of the amplitude of the relaxation time distribution (CY-a).
    [0064] [64] Fusion fracture behavior was determined by capillary rheometry. Capillary rheometry experiments were conducted at 190 ° C, using a double orifice capillary rheometer (Rosand RH-7, Malvern) operated in constant speed mode. A capillary mold 1 mm in diameter and 16 mm long and an orifice mold 1 mm in diameter were used during this study. The entry angle for the molds was 180 °, and the ratio of shrinkage from the reservoir drum to the die was about 15. Bagley and Rabinowitsch corrections were applied to obtain stable shear stresses as a function of the shear rate. . The stresses obtained from the capillarity experiments were compared with the magnitude of the measured complex modules of the dynamic frequency sweep measurement tests. The extrudates were collected at different shear rates and visualized using an optical microscope to identify the beginning and evolution of fusion fractures. Example 1
    [0065] [65] Four POL-IPs of the type described here were prepared as follows and named samples 1-4: Samples 1-3 were produced using the following polymerization procedure. All polymerization activities were carried out in a 1-gallon stainless steel reactor with 1.8 L of isobutane. Both metallocene solutions MTE-A and MTE-B were prepared with about 1 mg / ml in toluene. The structures of MTE-A and MTE-B used in the preparation of the samples are shown in figure 1. Alkyl aluminum (triisobutylaluminum, Tiba), fluoridated alumina, premixed MTE-A and MTE-B in the proportion shown were added in that order through a cargo port while isobutane vapor was subtly ventilated. The cargo door was closed and isobutane was added. The reactor contents were mixed and heated to an operating temperature of approximately 92 ° C, and ethylene was then introduced into the reactor with 1-hexene and hydrogen. Ethylene and hydrogen were fed according to demand, at a specified weight ratio to maintain the target pressure in the 390 psig reactor for 45 min. The reactor was maintained at the desired temperature during the activity by an automated heating-cooling system. Polymerization conditions and information on polymers 1-3 are summarized in Table 1.
    [0066] [66] Sample 4 was produced following the following polymerization procedure. All polymerization steps were carried out in a 1-gallon stainless steel reactor with 1.8 L of isobutane. Both metallocene solutions MTE-A and MTE-B were prepared with about 1 mg / ml in toluene. Alkyl aluminum (triisobutyl aluminum, Tiba), sulfated alumina, premixed MTE-A and MTE-B in the ratio shown were added in that order through a loading port while isobutane vapor was slowly vented. The cargo door was closed and isobutane was added. The reactor contents were mixed and heated to an operating temperature of about 92 ° C, and ethylene was then introduced into the reactor with 1-hexene and hydrogen. Ethylene and hydrogen were added according to demand, at a specified weight ratio to maintain the target pressure in the 390 psig reactor for 40 min. The reactor was maintained at the desired temperature during the activity by an automated heating-cooling system. Polymerization conditions and polymer information are summarized in Table 2. Two batches of polymers were produced and combined.
    [0067] [67] The molecular weight distribution profiles (MWD) of samples 1-4 are shown in Figure 2. Also shown in figure 2 is the profile of comparative sample A, which is high density polyethylene MARLEX H525, which is a resin chromium-based (Cr-based resin) commercially available from Chevron Philips Chemical Company LP.
    [0068] [68] The zero shear viscosity, relaxation time and rheological amplitude of the samples were determined and these data are shown in table 3. Table 3
    [0069] [69] Samples 1-4 demonstrated high rheological amplitudes and high viscosity at zero shear, suggesting fusion forces and processability of samples similar to Cr-based resins. In addition, Figure 3, which is a graph of viscosity as a function of frequency, shows that samples 1-4 revealed curves similar to Cr-based resins. Example 2
    [0070] [70] The fusion fracture behavior of POL-IPs has been investigated. Specifically, the fusion fracture behavior of samples 1-4 was evaluated via capillary rheometry and these data are presented in Table 4. Sample 1B and sample 2B were compositions prepared using the polymers of samples 1 and 2 respectively and a polymeric processing aid ( PPA) containing fluoropolymeric processing aids and fluorelastomers. Table 4
    [0071] [71] The results demonstrate that the magnitude of the Slip-stick oscillation of samples 1-4 (ie POL-IPs) is greater than that of Cr-based resins (ie sample A) indicating that samples 1-4 have a good fusion fracture potential. Samples 1-4 demonstrated a relatively low onset of soft - matte transition stresses that are similar to sample A and that can be attributed to the presence of HMW tails in these samples. In general, melting fracture behavior of samples 1-4 is expected to be similar to that of Cr-based resins.
    [0072] [72] Also, samples 1B and 2B containing PPA had a fusion fracture behavior characterized by a delay in the disappearance of the soft - matte transition and a reduction or disappearance of the slip-stick transition. ADDITIONAL DESCRIPTIONS
    [0073] [73] The following numbered modalities are provided as non-limiting examples.
    [0074] [74] An initial modality is a metallocene-catalyzed polymer containing (i) a higher molecular weight component (ii) a lower molecular weight component where the polymer has a polydispersity index of about 10 to about 26; a zero-shear viscosity of about 5x10 5 Pa.to about 2 x10 14 Pa.se a critical soft-matte transition tension of about 20 kPa to about 85 kPa under a shear rate of about 1, 5 s -1 to about 17 s -1 .
    [0075] [75] A second embodiment is a polymer of the first embodiment where the component with the highest molecular weight is present in an amount of about 3% w / w to about 30% w / w.
    [0076] [76] A third embodiment concerns the polymer of any of the first to second embodiments where the lowest molecular weight component is present in an amount of about 70% w / w to about 97% w / w.
    [0077] [77] A fourth modality is the polymer of any of the modalities from the first to the third having an average molecular weight of about 260 kg / mol to about 350 kg / mol.
    [0078] [78] A fifth modality is the polymer of any of the modalities from the first to the fourth having an average molecular weight number of about 12 kg / mol to about 26 kg / mol.
    [0079] [79] A sixth modality is the polymer of any of the modalities from the first to the fifth having an average molecular weight z of about 1500 kg / mol to about 2500 kg / mol.
    [0080] [80] A seventh modality is the polymer of any of the modalities from the first to the sixth having a short chain branch content of about 0.5 SCB / 1000C to about 3.5 SCB / 1000C in which of about 50% to about 80% of the short chain branches are located in the highest molecular weight component.
    [0081] [81] An eighth modality is that of the polymer of any of the modalities from the first to the seventh having long chain branches of about 0.002 branch per 1000 carbons to about 0.2 branch per 1000 carbons.
    [0082] [82] A ninth modality is the polymer of any of the modalities from the first to the eighth having a high charge melting index of about 5 to about 12.
    [0083] [83] A tenth modality is the polymer of any of the modalities from the first to the ninth having CY-a parameters of about 0.03 to about 0.4.
    [0084] [84] An eleventh modality is the polymer of any of the modalities from the first to the tenth having a tau eta value of about 7 s to about 2.0x10 5 s.
    [0085] [85] A twelfth modality is the polymer of any of the modalities from the first to the eleventh having a slipstick fracture magnitude of about 200 psi to about 1200 psi.
    [0086] [86] A thirteenth modality is the polymer of any of the modalities from the first to the twelfth having an N_100 value of about 0.2 to about 0.5.
    [0087] [87] A fourteenth modality is the polymer of any of the modalities from the first to the thirteenth having a viscosity at 100 rad / s of about 2x10 3 Pa.sa about 2, 4X10 3 Pa.s.
    [0088] [88] A fifteenth modality is a composition comprising the polymer of any of the modalities from the first to the fourteenth and a polymer processing aid.
    [0089] [89] A sixteenth modality is the polymer of any of the modalities from the first to the fifteenth where the polymeric processing aid comprises fluoroelastomers, polyethylene glycol, low molecular weight waxes, or a combination thereof.
    [0090] [90] A seventeenth modality is an article made from a polymer of any of the modalities from the first to the sixteenth.
    [0091] [91] An eighteenth modality is the composition of the fifteenth modality.
    [0092] [92] A nineteenth modality is a dual metallocene-catalyzed polyethylene comprising (i) a higher molecular weight component and (ii) a lower molecular weight component where the polymer has a polydispersity of about 10 to about of 26; a zero-shear viscosity of about 5x10 5 Pa.sa about 2 x10 14 Pa.se a soft matte transition tension of about 20 kPa and about 85 kPa at a shear rate of about 1.5 s -1 and 17 s -1 .
    [0093] [93] A twentieth modality is a composition containing a polyethylene catalyzed by dual metallocene of the nineteenth modality and a fluoroelastomer.
    [0094] [94] A twenty-first modality is a tube made of a composition of any of the modalities from the twenty to the twenty-first modality.
    [0095] [95] A twenty-second modality is a polymer of any of the modalities from the first to the twelfth modality where the polymer is a copolymer of ethylene and 1-hexene.
    [0096] [96] Although disclosure modalities have been shown and described, modifications can be made without departing from the spirit and teachings of the disclosure. The modalities described here are only exemplary, and are not intended to be limiting. Many variations and modifications to the disclosure disclosed herein are possible and are within the scope of the description. When numerical ranges or limitations are expressly stated, those expressed ranges or limitations should be understood to include iterative ranges or limitations of the same magnitude expressly stated (for example, from about 1 to about 10 includes, 2, 3, 4 etc .; above 0.10 includes 0.11, 0.12, 0.13, etc.). For example, whenever a numerical range with a lower limit N i , and an upper limit, N u , is disclosed, any numbers falling within the range are specifically disclosed. In particular, the following numbers within the range are specifically disclosed: N = N L + k * (N u -N i ), where k is a variable ranging from 1 percent to 100 percent with an increase of 1 percent, or 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 N 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 object element is required, or alternatively, is not required. Both alternatives are intended to be within the scope of the claim. Use of broader terms such as, understands, includes, owning, etc. are to be understood to provide support for narrower terms, such as consisting of, consisting essentially of, substantially comprised of, etc.
    权利要求:
    Claims (22)
    [0001]
    Metallocene-catalyzed polymer characterized by comprising (i) a higher molecular weight component and (ii) a lower molecular weight component, in which the polymer has a polydispersity index of 10 to 26; a zero shear viscosity of 5x10 5 Pa.sa 2 x10 14 Pa.se a critical transition stress from soft to matte from 20kPa to 85 kPa at a shear rate of 1.5 s -1 to 17 s -1 .
    [0002]
    Polymer according to claim 1, characterized by the fact that the highest molecular weight component is present in an amount of 3% w / w to 30% w / w.
    [0003]
    Polymer according to claim 1, characterized in that the lowest molecular weight component is present in an amount of 70% w / w and 97% w / w.
    [0004]
    Polymer according to claim 1, characterized in that it has a weight average molecular weight of 260 kg / mol to 350 kg / mol.
    [0005]
    Polymer according to claim 1, characterized in that it has a numerical average molecular weight of 12 kg / mol to 26 kg / mol.
    [0006]
    Polymer according to claim 1, characterized in that it has an average molecular weight z of 1500 kg / mol to 2500 kg / mol.
    [0007]
    Polymer according to claim 1, characterized by having a short chain branch content of 0.5 SCB / 1000C to 3.5 SCB / 1000C, in which 50% to 80% of the short chain branches are located in the highest molecular weight component.
    [0008]
    Polymer according to claim 1, characterized in that it has a long chain branch content of 0.002 branch per 1000 carbons to 0.2 branch per 1000 carbons.
    [0009]
    Polymer according to claim 1, characterized by having a high charge melting index of 5 to 12.
    [0010]
    Polymer according to claim 1, characterized in that it has a CY-a parameter of 0.03 to 0.4.
    [0011]
    Polymer according to claim 1, characterized in that it has a tau eta value of 7 s at 2.0x10 5 s.
    [0012]
    Polymer according to claim 1, characterized by having a slip-stick fracture magnitude of 200 psi to 1200 psi.
    [0013]
    Polymer according to claim 1, characterized in that it has an N_100 value of 0, 2 to 0, 5.
    [0014]
    Polymer according to claim 1, characterized in that it has a viscosity at 100 rad / s of 2x10 3 Pa.sa 2, 4x10 3 Pa.s.
    [0015]
    Composition characterized by comprising the polymer, as defined in claim 1, and a polymeric processing aid.
    [0016]
    Composition according to claim 15, characterized in that the polymeric processing aid comprises fluorelastomers, polyethylene glycol, low molecular weight waxes or combinations thereof.
    [0017]
    Article characterized by being made of the polymer as defined in claim 1.
    [0018]
    Article characterized by being made of the composition as defined in claim 15.
    [0019]
    Dual metallocene-catalyzed polyethylene characterized by comprising (i) a higher molecular weight component, and (ii) a lower molecular weight component, where the polymer has a polydispersity index of 10 to 26; a zero shear viscosity of 5x10 5 Pa.sa 2 x10 14 Pa.se a smooth to matte transition tension of 20kPa to 85kPa at a shear rate of 1.5 s -1 to 17 s -1 .
    [0020]
    Composition characterized by comprising dual metallocene-catalyzed polyethylene, as defined in claim 19, and a fluorelastomer.
    [0021]
    Tube characterized by being made of the composition as defined in claim 20.
    [0022]
    Polymer according to claim 1, characterized in that it is a copolymer of ethylene and 1-hexene.
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    法律状态:
    2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-12-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-04-22| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-06-30| 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 25/02/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US13/778,693|US8815357B1|2013-02-27|2013-02-27|Polymer resins with improved processability and melt fracture characteristics|
    US13/778,693|2013-02-27|
    PCT/US2014/018243|WO2014134015A1|2013-02-27|2014-02-25|Polymer resins with improved processability and melt fracture characteristics|
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