• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Method for Making Film and Film The present invention is a method for producing a film particularly suitable for shrink film applications, said method comprising the steps of selecting a target polyethylene resin and then increasing the melt strength of the polyethylene resin by reacting with the resin. of polyethylene with an alkoxyamine derivative, and then form a film of the reacted target polyethylene.
    公开号:BR112012017118B1
    申请号:R112012017118-6
    申请日:2011-01-11
    公开日:2019-11-19
    发明作者:Gomes Jorge；Demirors Mehmet；Terrasa Michael；Mazzola Nicolas；Karjala Teresa
    申请人:Dow Brasil Sa；Dow Global Technologies Llc；
    IPC主号:
    专利说明:

    “METHOD TO PRODUCE FILM AND FILM
    Field of the invention [0001] The present invention generally relates to ethylene / alpha-olefin interpolymer resins for making films with improved optical properties (opacity, gloss and / or transparency), good mechanical properties (tearing and perforation) and high shrinkage (shrinkage stress), which creates valuable films, especially for shrinkable applications, such as collation shrink films.
    Background and summary of the invention [0002] Polyethylene has desirable properties that helped it become the highest volume polymer ever manufactured. It can be prepared in different processes, so that it can provide different properties. Known polyethylene families include high density polyethylene (HDPE), linear low density polyethylene (LLDPE) and low density polyethylene manufactured using high pressure reactors (LDPE). In these broad classes there are many variations resulting from different types of polyolefin process technology (for example, in solution, in paste or gaseous phase) or from the use of different catalysts (for example, ZieglerNatta or constricted geometry catalysts). The desired application requires a careful balance of rheological properties that lead one skilled in the art to select one type of polyethylene over another. In many applications, such as blow molding and blown film, polyethylene melt strength is a key parameter.
    [0003] The melt strength is a practical measurement that
    Petition 870190091036, of 9/13/2019, p. 12/57
    2/41 can predict material performance. In melt processing, good melt strength is important to maintain stability during processes, such as coating, blown film production, fiber spinning and foamed parts.
    [0004] The melt strength is related to several processing parameters, such as bubble stability and, therefore, thickness variation during blown film production; parison formation during blow molding; bending during profile extrusion; formation of cells during foaming; more stable thickness distribution during sheet / film thermoforming.
    [0005] This property can be improved by using higher molecular weight resins, although such resins generally require more robust equipment and greater energy use, as they tend to generate higher extrusion pressure during the extrusion process. Therefore, properties must be balanced to provide an acceptable combination of physical properties and processability.
    [0006] The present invention generally relates to ethylene / alpha-olefin interpolymer resins that can form films with improved optical properties (opacity, gloss and / or transparency), good mechanical properties (tearing and perforation) and high shrinkage ( shrinkage tension), which provides high quality, especially for shrink films, such as collation shrink films. Additionally, a high modulus is an advantage factor. It is difficult to obtain a balance of these properties with a resin. For example, high retraction can be achieved by weight
    Petition 870190091036, of 9/13/2019, p. 13/57
    3/41 very high molecular. This high molecular weight, however, often results in unsatisfactory optical properties, since materials with very high molecular weight tend to be highly elastic and by extrusion create high surface roughness on the film, which leads to lower optical properties. Another example is that generally to increase the modulus, it is necessary to increase the density. When density is increased, however, the drilling properties generally decrease.
    [0007] Additionally, the present invention allows the use of an existing polyethylene resin, which when reacted with an alkoxyamine derivative, is even more suitable for shrink films due to the lower melting index (I 2 or MI), resistance to higher melt, higher viscosity ratios, and higher melt index ratios (I10 / I2).
    [0008] The ethylene / alpha-olefin interpolymer of the present invention provides good properties (such as optics, tearing, perforation, shrinkage and modulus) without any of these properties being unduly negatively impacted. The present invention consists of a new process to increase the resistance of polyethylene melt, involving reacting melted polyethylene with an alkoxamine derivative, through regular extrusion processing. Consequently, an aspect of the invention consists of a method for increasing the melt strength of a polyethylene resin comprising first selecting a polyethylene resin with a density, determined according to ASTM D792, in the range of 0.90 g / cm 3 to 0 , 955 g / cm 3 , and a melting index, determined according to ASTM D1238 (2.16 kg, 190 ° C)
    Petition 870190091036, of 9/13/2019, p. 14/57
    4/41 in the range of 0.01 g / 10 min to 10 g / 10 min and then react an alkoxyamine derivative with the polyethylene resin in an amount and under conditions sufficient to increase the melt strength of the polyethylene resin.
    [0009] The present invention consists of a new process for increasing the melt strength of polyethylene, involving reacting melted polyethylene with an alkoxamine derivative through regular extrusion processing. Accordingly, an aspect of the invention consists of a method for increasing the melt strength of a polyethylene resin comprising first selecting a polyethylene resin with a density, determined according to ASTM D792, in the range of 0.90 g / cm3 to 0, 955 g / cm3, and a melting index, determined according to ASTM D1238 (2.16 kg,
    190 ° C) in the range of 0.01 g / 10 min to 10 g / 10 min and then react an alkoxyamine derivative with the polyethylene resin in an amount and under conditions sufficient to increase the melt strength of the polyethylene resin.
    [0010] The present invention can also increase the Viscosity Ratio of the resin, indicating good processability. Detailed description of the invention [0011] In its broadest sense, the present invention consists of a method for producing improved films suitable for shrink applications, wherein the method involves increasing the melt strength of a target polyethylene resin. The polyethylene resin includes all polymers or polymer mixtures derived from at least 50% by weight of ethylene monomer units. Includes materials known in the art such as high density polyethylene (HDPE), linear low density polyethylene
    Petition 870190091036, of 9/13/2019, p. 15/57
    5/41 (LLDPE), and low density polyethylene prepared using high pressure reactors (LDPE).
    [0012] The selected target polyethylene resin must have a density, determined according to ASTM D792, in the range of 0.90 g / cm3 to 0.955 g / cm3, more preferably from 0.92 g / cm 3 to 0 , 94 g / cm 3 , even more preferably from 0.923 g / cm 3 to 0.935 g / cm 3 and a melting index, determined according to ASTM D1238 (2.16 kg, 190 ° C) in the range of 0.01 g / 10 min to 10 g / 10 min, more preferably from 0.1 g / 10 min to 7 g / 10 min. Suitable polyethylene resins can be produced with conventional Ziegler Natta or Chromium catalysts, but also with metallocene or single-site catalysts. Such resins can have monomodal or multimodal molecular weight distributions.
    [0013] Once the target polyethylene resin is selected, it is reacted with an alkoxyamine derivative. For the purposes of the present invention, alkoxyamine derivatives include nitroxide derivatives. The alkoxyamine derivative is added in an amount and under sufficient conditions to increase the melt strength of the polyethylene resin. The alkoxiamine derivatives correspond to the formula:
    (R1) (R 2 ) NO-R3 where R1 and R2 are each independently hydrogen, C4-C42 alkyl or C4-C42 aryl or substituted hydrocarbon groups comprising O and / or N, and where R1 and R2 can forming a ring structure together; and where R3 is hydrogen, a hydrocarbon or substituted hydrocarbon group comprising O and / or N. Preferred groups for R3 include -C1-C19 alkyl; aryl -C6-C10; -C2-C19 alkenyl; -C1-C19 alkyl; -O-C6-C10 aryl; -NH- C1-C19 alkyl; -NH-arila
    Petition 870190091036, of 9/13/2019, p. 16/57
    6/41
    C 6 -Ci 0 ; -N- (C 1 -C 9 alkyl) 2 . R3 most preferably contains an acyl group.
    [0014] The preferred compound can form nitroxyl radical (R1) (R2) N-O * or aminyl radical (R1) (R2) N * after decomposition or thermolysis.
    [0015] A particularly preferred species of alkoxyamine derivative is 9- (acetyloxy) -3,8,10triethyl-7,8,10-trimethyl-1,5-dioxa-9-azaspiro [5.5] octadecanoate -3yl] methyl which has the following chemical structure:
    [0016] Examples of some preferred species for use in the present invention include the following:
    [0017] In general, hydroxylamine esters are more preferred, with one being particularly preferred:
    9- (acetyloxy) -3,8,10-triethyl-7,8,10 trimethyl-1 r 5-dioxa-9-azaspiro [5 r 5] undec-3-yl] methyl octadecanoate.
    [0018] Alkoxyamine derivatives are added in sufficient quantity to increase melt strength
    Petition 870190091036, of 9/13/2019, p. 17/57
    7/41 and / or extensional viscosity to the desired level. In general, alkoxyamine derivatives are added in an amount of 1 to 900 ppm of the total amount of polyethylene polymer by weight (from 1 to 900 parts of alkoxyamine derivative per one million parts (by weight) of target resin plus carrier resin. , if any), more preferably from 15 to 600 ppm, more preferably from 25 to 400 ppm and even more preferably from 30 to 200 ppm.
    [0019] The addition to the polyethylene polymer can be carried out in all common mixers, in which the polymer is melted and mixed with the additives. Suitable mixing machines are known in the art. They are predominantly mixers, kneaders and extruders.
    [0020] The process is preferably conducted in an extruder by introducing the additive during processing. Particularly preferred processing machines are mono-screw extruders, counter-rotating and counter-rotating twin-screw extruders, planetary extruders, ring extruders and co-kneaders. It is also possible to use processing machines equipped with at least one gas removal compartment to which a vacuum can be applied. Suitable extruders and kneaders are described, for example, in Handbuch der Kuntstoftextrusion, Vol 1 Grundlagen, Editors F.Hensen, W.Knappe, H.Potente, 1989, p.3-7, ISBN.3-446-14339-4 ( vol. 2 Extrusionsanlagen 1986, ISBN 3-446-14329-7). For example, the thread length can be 1-60 times the thread diameter, preferably 3548 times the thread diameters. The rotational speed of the thread is preferably 10-600 revolutions per minute (rpm),
    Petition 870190091036, of 9/13/2019, p. 18/57
    8/41 more preferably 25-300 rpm. It is also possible to first prepare a concentrated mixture of the additive in a polyethylene-bearing resin, preferably from 1000 to 10000 ppm, and then introduce that concentrate, or standard batch via extruder, into a molten polyethylene using a static mixer to mix the two materials, preferably from 1 to 20% by weight of the concentrate in the molten resin. The concentrate can be processed in an extruder, preferably at temperatures of 180 to 240 ° C. Temperatures in the static mixer can vary from 200 to 250 ° C, with a residence time in the mixer ranging from 1 to 10 minutes.
    [0021] Maximum performance depends on the thread diameter, rotational speed and driving force. The process of the present invention can also be carried out at a level below the maximum yield, by varying the mentioned parameters or using weighing instruments that release metered quantities.
    [0022] If a plurality of components are added, they can be pre-mixed or added individually.
    [0023] Polymers need to be subjected to a high temperature for a period of time sufficient for the desired changes to occur. The temperature is generally above the softening point of the polymers. In a preferred embodiment of the process of the present invention, a temperature range of less than 280 ° C, particularly from about 160 ° C to 280 ° C, is employed. In a particularly preferred process variant, the temperature range of about 200 ° C to 270 ° C is used.
    Petition 870190091036, of 9/13/2019, p. 19/57
    9/41 [0024] The time period required for reaction can vary as a function of temperature, the amount of material to be reacted and the type of extruder used, for example. The time usually ranges from about 10 seconds to 30 minutes, particularly from 20 seconds to 20 minutes.
    [0025] The alkoxyamine derivative can advantageously be added to the mixing device using a standard batch. As will be appreciated by those skilled in the art, the carrier resin for the standard batch must be selected to be compatible with the resin to be modified. LDPE high pressure and low density polyethylene polymers (referred to in the industry as LDPE) unexpectedly proved to be the preferred carrier due to their lower reactivity, as demonstrated by the small variation in extrusion pressure during the production of the standard batch. HDPE can be a better carrier, since it reacts even less because it does not have tertiary carbons and very low vinyl content. Another advantage of the present invention is the discovery that polypropylene is not a good carrier for this additive, as it tends to degrade at typical processing temperatures. Another finding is that the carrier resin must be substantially free of any antioxidant additives, which means that the carrier resin must preferably have less than 1,000 ppm of antioxidant additives, preferably less than 500 ppm and more preferably less than 100 ppm by weight, since that antioxidants tend to suppress the activity of the additive.
    [0026] The preferred carrier resin must be compatible with manual application; it must have a viscosity similar to that of the target polyethylene resin with which it will be mixed. It should
    Petition 870190091036, of 9/13/2019, p. 20/57
    10/41 is preferably an LDPE or HDPE resin with minimal tri-substituted unsaturation units, preferably less than 70 per 1,000,000 carbons. The preferred carrier resin must have a molecular weight (Mn) of less than 50,000, so that it is easy to process, as demonstrated by the pressure drop in the extruder. The carrier resin must incorporate other additives for processing aids, although it must be substantially free of antioxidant compounds, preferably containing less than 1,000 ppm, preferably less than 500 ppm, more preferably less than 100 ppm by weight of any antioxidant compound.
    [0027] The target polyethylene resin can be an ethylene copolymer with any alkene monomer containing from 3 to 12 carbons. Preferably, the target polyethylene resin should have a level of tri-substituted unsaturation units per 1,000,000 carbon atoms ranging from 200 to 450. It should have a slightly lower molecular weight than the carrier resin, measured by the melt index ( g / 10 min). Preferably, the melt index of the polyethylene resin should be 0.2-0.5 units (g / 10 min) higher than the final desired resin. Preferably, the polyethylene resin should contain minimal or no amount of antioxidant additives and any additives should be well dispersed in the resin before being mixed with the carrier resin.
    [0028] The amount of the active alkoxyamine-derived material in the carrier resin should be in the range of 0.1 to 30% by weight, preferably from 0.1 to 5%, and more preferably in the range of 0.2 to 1%. The standard batch quantity is added so that the alkoxyamine derivative is added to the target product in the range of 10 to 900 ppm, preferably 15 to 600
    Petition 870190091036, of 9/13/2019, p. 21/57
    11/41 ppm, more preferably from 25 to 400 ppm, and even more preferably from 30 to 200 ppm. It will be easily understood by those skilled in the art that the amount of alkoxyamine derivative in the final product will be reduced by the amounts added, as the compound reacts with the target and carrier polyethylene.
    [0029] Preferably, the amount of the alkoxamine derivative should be kept below about 100 ppm to minimize the reaction in the carrier resin, reduce the potential for gels to form in the final product, and be substantially reacted in the final product so that it remains stable in case of additional processing. It should be understood that after the alkoxamine derivative reacts with the target resin, it may be desirable to add one or more antioxidant additives, to protect the properties of the modified target resin. One way to achieve this is to mix the resin after reaction with the alkoxyamine derivative with another resin that is rich in antioxidants.
    Mixture [0030] The target polyethylene for use in the present invention can advantageously be a mixture of two or more polymers, for example, a linear low density polyethylene mixed with a composition of high pressure and low density polyethylene (LDPE). Such a low density polyethylene composition can have a density in the range 0.910 g / cm 3 to 0.940 g / cm 3 ; for example, from 0.915 g / cm 3 to 0.935 g / cm 3 , and a melting index (I2) in the range of 0.1 to 5 g / 10 minutes; for example, from 0.2 to 2g / 10 minutes. The total mixture of the target resin before reacting with the alkoxamine derivative may have a density in the range of 0.910 g / cm 3 at
    Petition 870190091036, of 9/13/2019, p. 22/57
    12/41
    0.940 g / cm 3 ; for example, from 0.915 g / cm 3 to 0.935 g / cm 3 , and a melting index (I 2 ) in the range of 0.01 to 5 g / 10 minutes; for example, from 0.1 to 3g / 10 minutes. Alternatively, the target resin (which may itself be a mixture) can be first reacted with the alkoxyamine derivative and then mixed with one or more additional polymers.
    Film Application [0031] The polyethylene of the invention or its mixture with one or more other polymers, for example, LDPE, can advantageously be used to manufacture films. These films may include, but are not restricted to high transparency shrink films, shrink films for packaging units, flat stretch films, silage films, protective stretch films, sealants, sachet films, coating films, films oriented in the direction of machine, and base diaper support sheets. Different methods can be used to make such films. Appropriate conversion techniques include, but are not limited to, blown film process, flat film process, stretching process, double bubble process, such as the vertical or horizontal forming, filling and closing process, partially cross-linked or non-cross-linked.
    [0032] Such techniques are generally well known. In one embodiment, the conversion technique includes, although it is not restricted to the blown film process.
    [0033] Films according to the present invention may include at least one layer of film, such as a monolayer film, or at least one layer in a multilayer film prepared by flat die, blow, calender, or extrusion coating processes. . Target polyethylene
    Petition 870190091036, of 9/13/2019, p. 23/57
    13/41 reacted or a mixture thereof, with one or more other polymers, for example, LDPE, can be used in a variety of films, including, although not restricted to high transparency shrink films, shrink films for packaging unitization , flat stretch films, silage films, protective stretch films, sealants, sachet films, coating films, machine-oriented films, and diaper support sheets.
    TEST METHODS
    Melt Resistance [0034] Melt resistance measurements are conducted on a Goettfert Rheotens 71.97 instrument (Goettfert Inc .; Rock Hill, SC), connected to a Goettfert Rheotester 2000 capillary rheometer. The fused sample (about 25 to 30 grams) is fed with a Goettfert Rheotester 2000 capillary rheometer, equipped with a flat entry angle (180 degrees) 30mm in length and 2.0mm in diameter and an aspect ratio (length / diameter) of 15. After balancing the samples at 190 ° C for 10 minutes, the piston is driven at a constant speed of 0.265 mm / second. The standard test temperature is 190 ° C. The sample is pulled uniaxially against a set of accelerated compression cylinders located 100 mm below the matrix, with an acceleration of 2.4 mm / s 2 . The pulling force is recorded as a function of the pickup speed of the compression cylinders. The melt strength is reported as the plateau strength (cN) before the filament breaks. The conditions described below are used in the melt strength measurements; piston speed = 0.265 mm / second; disk acceleration - 2.4 mm / s 2 ; capillary diameter = 2.0mm; length of
    Petition 870190091036, of 9/13/2019, p. 24/57
    Capillary 14/41 = 30mm; and barrel diameter = 12mm.
    Melting Index [0035] The melting index, or I 2 , is measured according to ASTM D 1238, Condition 190 ° C / 2.16 kg, and is reported in grams eluted for 10 minutes. I 10 is measured according to ASTM D1238, Condition 190 ° C / 10 kg, and reported in grams.
    Density [0036] Samples for density measurements are prepared according to ASTM D 4703-10. The samples are pressed at 374 ° F (190 ° C) for five minutes at 10,000 psi (68 MPa). The temperature is maintained at 374 ° F (190 ° C) for the five minutes mentioned above, and then the pressure is increased to 30,000 psi (207 MPa) for three minutes. This condition is maintained for one minute at 70 ° F (21 ° C) and 30,000 psi (207 MPa). Measurements are made within one hour of pressing the sample using ASTM D792-08, Method B. Dynamic Mechanical Spectroscopy [0037] The resins are molded by compression on 3mm thick x 1 ”circular plates at 350 ° F for five minutes, under 1500 psi air pressure. The sample is then removed from the press and placed on the bench to cool.
    [0038] A frequency scan at constant temperature was performed using an ARES system - Advanced Rheometric Expansion System from TA Instruments, equipped with parallel plates of 25mm (diameter), under nitrogen purge. The sample was placed on the plate, and allowed to melt for five minutes at 190 ° C. The plates are then closed in a 2mm gap / gap, the trimmed sample (the excess sample that extends beyond the 25mm diameter circumference of the plate is removed) and then the
    Petition 870190091036, of 9/13/2019, p. 25/57
    15/41 test. The method has an additional delay of five minutes, to allow temperature equilibrium. The tests are conducted at 190 ° C in a frequency range of 0.1 to 100 rad / s. The strain range is constant at 10%. The voltage response is analyzed in terms of amplitude and phase, from which the storage module (G z ), loss module (G), complex module (G *), complex viscosity η *, tan (δ) or tan delta, viscosity at 0.1 rad / s (V0.1), viscosity at 100 rad / s (V100), and the Viscosity Ratio (V0.1 / V100).
    Triple Detection Gel Permeation Chromatography (TDGPC)
    - Conventional GPC, GPC with Light Scattering and gpcBR [0039] For the techniques used here (conventional GPC, GPC with Light Scattering, and gpcBR), a Triple Detection Gel Permeation Chromatography system (3D- GPC or TDGPC). This system consists of a high temperature 150 ° C chromatograph from Waters (Milford, Mass) (other suitable high temperature GPC instruments include models 210 and 220 from Polymer Laboratories (Shropshire, UK) equipped with a dispersion detector of laser light (LS) in 2 angles, model 2040 from Precision Detectors, an infrared detector from Polymer ChAR (Valencia, Spain) and a Viscotek 150R (DP) 4 capillary solution viscometer (Houston, Texas).
    [0040] A GPC with these last two independent detectors and with at least one of the detectors first mentioned is sometimes referred to as 3D-GPC or TD-GPC, while the term GPC alone generally refers to the conventional GPC. Data collection is performed using Viscotek TriSEC software, Version 3, and a
    Petition 870190091036, of 9/13/2019, p. 26/57
    16/41
    DM400 Data Manager Viscotek 4 channels. The system is also equipped with an online solvent degassing device from Polymer Laboratories (Shropshire, United Kingdom).
    [0041] The eluent from the GPC column assembly flows through each detector arranged in series, in the following order: LS detector, IR4 detector, and then DP detector. The systematic approach for determining deviations from the multidetector is conducted in a manner consistent with that published by Balke, Mourey, et al. (Mourey and Balke, Chromatography Polym., Chapter 12 (1992)) (Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym., Chapter 13 (1992), optimizing the logarithmic results of the triple detector (MW and intrinsic viscosity) to use a wide polyethylene standard, as described in the paragraph dedicated to GPC with Light Scattering (LS) below in the paragraph after Equation (5).
    [0042] Appropriate high temperature GPC columns can be used such as four 13 micron and 30 cm long Shodex HT803 columns or four 30 cm columns from Polymer Labs containing 20 micron mixed pore size load (MixA LS, Polymer Labs ). MixA LS columns are used here. The sample carousel compartment is operated at 140 ° C and the column compartment is operated at 150 ° C. The samples are prepared at a concentration of 0.1 gram of polymer in 50 milliliters of solvent. The chromatographic solvent and the sample preparation solvent is 1,2,4-trichlorobenzene (TCB) containing 200 ppm 2,6-di-terbutyl-4-methylphenol (BHT). The solvent is sparged with nitrogen. The polymer samples are slightly agitated at 160 ° C for four hours. The injection volume is 200
    Petition 870190091036, of 9/13/2019, p. 27/57
    17/41 microliters. The flow rate through the GPC system is adjusted to 1 ml / minute.
    Conventional GPC [0043] For conventional GPC, the IR4 detector is used and the GPC column set is calibrated using 21 polystyrene standards with narrow molecular weight distribution. The molecular weight (MW) of the standard ranges from 580 g / mol to 8,400,000 g / mol and the standards are contained in six cocktail mixtures. Each standard mixture has at least a decade of separation between the individual molecular weights. Standard blends are purchased from Polymer Laboratories. Polystyrene standards are prepared at 0.025g in 50ml of solvent for molecular weights equal to or greater than 1,000,000 g / mol and at 0.05g in 50ml of solvent for molecular weights less than 1,000,000 g / mol. The polystyrene standards are dissolved at 80 ° C with slight agitation for 30 minutes. Mixtures of narrow standards are operated first and in decreasing order of the highest molecular weight component to minimize degradation. The molecular weights, peak polystyrene standard are converted to molecular weights of polyethylene using Equation (1) (as described in Williams and Ward, J. Polym. Sci. Polym. Let., 6, 621 (1968)):
    M polyethylene A (M polystyrene) B (Eq · 1 ) where M is the molecular weight of polyethylene or polystyrene (as marked) and B is equal to 1.0. The person skilled in the art knows that A can be in the range of about 0.38 to about 0.44, and that it is determined at the time of calibration using a wide polyethylene standard, as described in the paragraph dedicated to GPC with Light Scattering (LS) below on
    Petition 870190091036, of 9/13/2019, p. 28/57
    18/41 paragraph after Equation (5). The use of this polyethylene calibration method to obtain molecular weight values, such as the molecular weight distribution (MWD or Mw / Mn) and related statistics, is defined herein as the modified Williams and Ward method. The numerical average molecular weight, the weight average molecular weight and the z-average molecular weight are calculated based on the following equations:
    Mw cc = Σ (Eq. 2) (Eq. 3)
    M z , cc = Σ tX .. ·) / Σ) (Eq. 4)
    Light Scattering GPC (LS) [0044] For GPC LS, the PD12040 model detector is used
    Precision Detector 2040. Depending on the sample, the 15 ° or 90 ° angle of the light scattering detector is used for calculation purposes. Here, the 15 ° angle is used.
    [0045] Molecular weight data are obtained in a manner compatible with that published by Zimm (Zimm, BH, J.Chem.Phys., 16, 1099 (1948) and Kratochvil (Kratochvil, P., Classical Light Scattering from Polymer Solutions , Elsevier, Oxford, NY (1987)).
    [0046] The total injected concentration used in determining the molecular weight is obtained from the mass detector area, and the mass detector constant derived from an appropriate linear polyethylene homopolymer, or one of the weight average molecular weight polyethylene standards known. The calculated molecular weights are obtained using a light scattering constant derived from one or more of the
    Petition 870190091036, of 9/13/2019, p. 29/57
    19/41 polyethylene standards mentioned below, and a refractive index concentration coefficient, dn / dc, of 0.104. Generally, the response of the mass detector and the light scattering constant should be determined from a linear pattern with a molecular weight exceeding about 50,000 g / mol. Calibration of the viscometer can be performed using the methods described by the manufacturer, or alternatively using the values of appropriate published linear standards, such as '' Standard Reference Materials (SEM) 1475a (from the National Institute of Standards and Technology (NTS) Chromatographic concentrations are considered too low to eliminate the treatment of second coefficient virial effects (concentration effects on molecular weight).
    [0047] With 3D-GPC, the absolute weight average molecular weight ("Mw, Abs") is determined using Equation (5) below, and using the ’’ peak area ”method to obtain greater accuracy and precision. The ’’ Area LS ’and’ ’Area Cone.
    = ^ c ~ ii
    LS Area
    Cone. Area (Eq.5) [0048] For each LS profile (for example, see Figures 1 and 2), the x-axis (MWcc-CPC log), where cc refers to the conventional calibration curve, is determined as described in follow. First, the polystyrene standards (see above) are used to calibrate the retention volume in ”MW PS logarithmic. Then, Equation 1 (Mp O i ie tii e no = A x (Mp Olies tir e no) B ) is used to convert ”MW PS logarithmic” to ”MW PE
    Petition 870190091036, of 9/13/2019, p. 30/57
    20/41 logarithmic. The logarithmic MW PS scale serves as an eixox for the LS profiles of the experimental section (the logarithmic MW PS is equivalent to the MW log (cc-CPC)). The y-axis for each LS profile is the response of the LS detector normalized by the injected mass sample. Initially, the molecular weight and intrinsic viscosity for a linear polyethylene standard sample, such as SRM1475a or equivalent, are determined using conventional calibrations (cc) for both molecular weight and intrinsic viscosity as a function of elution volume.
    [0049] In the low molecular weight region of the GPC elution curve, when the presence of a significant peak known to be caused by the presence of antioxidant or other additives, the presence of such peak causes an underestimation of the numerical average molecular weight (Mn) of the polymer sample and polydispersity overvaluation of the sample defined as Mw / Mn, where Mw is the weight average molecular weight. The actual molecular weight distribution of the polymer sample can therefore be calculated from the elution of GPC,
    excluding yourself that extra peak. That process is usually described as The feature in exclusion peak we procedures in processing in data in analysis in
    liquid chromatography. In this process, such an additive peak is excluded from the GPC elution curve before the calculation of the molecular weight of the sample is performed from the GPC elution curve.
    GpcBR Branching Index through GPC with Triple Detector (3D-GPC) [0050] The gpcBR branching index is determined by first calibrating light scattering, viscosity,
    Petition 870190091036, of 9/13/2019, p. 31/57
    21/41 and concentration detectors, as previously described. The baselines are then subtracted from the light scattering, viscometer and concentration chromatograms. Integration windows are then adjusted to ensure integration of all low molecular weight retention volume ranges in the light scattering and viscometer chromatograms that indicate the presence of polymer detectable from the refractive index chromatogram. Linear polyethylene standards are then used to establish Mark-Houwink constants of polyethylene and polystyrene. When obtaining the constants, the two values are used to construct two conventional linear reference calibrations for polyethylene molecular weight and intrinsic polyethylene viscosity as a function of elution volume, as shown in Equations (6) and (7):
    M PE -
    Kk /
    KpE)
    (Eq.6)
    (Eq.7) [0051]
    GpcBR branching index is a robust method for characterizing long chain branching as described in Yau, Wallace W., '' Examples of Using 3D-GPC - TREE for Polyolefin Characterization, ”Macromol. Symp., 2007, 257, 29-45. The index avoids the 3D-GPC "slice-by-slyce" (portion by portion) calculations traditionally used in the determination of g z values and in branch frequency calculations, in favor of the total polymer detector areas. From the data of
    Petition 870190091036, of 9/13/2019, p. 32/57
    22/41
    3D-GPC, it is possible to obtain the absolute weight average molecular weight of the sample volume (Mw, Abs) r through the light scattering detector (LS) r using the peak area method. The method avoids the slice-by-slice ratio of the light scattering detector signal to the concentration detector signal, required in a traditional g z determination . [0052] With 3D-GPC, the sample's intrinsic viscosities are also obtained regardless of the use of Equations (8). The area calculation in Equation (5) and (8) offers greater precision, since it is a global sample area, it is much less sensitive to the variation caused by the noise of the detector and the adjustments in the 3D-GPC in the limits of baseline and integration. Most importantly, the peak area calculation is not affected by deviations in the detector volume. Similarly, the high precision intrinsic viscosity of the sample (IV) is obtained by the area method shown in Equation (8):
    DP Area
    Cone. Area (Eq.8) where DPi means the differential pressure signal directly monitored from the online viscometer.
    [0053] To determine the gpcBR branching index, the light scattering elution area for the polymer sample is used to determine the molecular weight of the sample. The elution area of the viscosity detector for the polymer sample is used to determine the intrinsic viscosity (IV or [η]) of the sample.
    [0054] Initially, the molecular weight and viscosity
    Petition 870190091036, of 9/13/2019, p. 33/57
    23/41 intrinsic for a standard linear polyethylene sample, such as SRM1475a or equivalent, are determined using conventional calibrations (cc) for both molecular weight and intrinsic viscosity as a function of elution volume, according to Equations ( 2) and (9):
    [7] cc -
    IVi (Eq.9) [0055] Equation (10) is used to determine the gpcBR branching index:
    gpcBR =
    ÍMcc) [7] J (Eq.10) [0056] where [η] is the measured intrinsic viscosity, [T |] C c θ the intrinsic viscosity of conventional calibration, Mw is the measured average molecular weight and M w . cc is the weight average molecular weight of conventional calibration. The weighted average molecular weight by light scattering (LS) using Equation (5) is commonly referred to as '' absolute weighted average molecular weight ”or M w , Abs.” OM w . cc of Equation (2) using the conventional GPC molecular weight calibration curve ('' conventional calibration ') is often referred to as'' main polymer chain molecular weight '', '' conventional weight average molecular weight ”and” M w , G p C.
    [0057] All statistical values with the subscript ”cc” are determined using their respective elution volumes, the corresponding conventional calibration as
    Petition 870190091036, of 9/13/2019, p. 34/57
    24/41 previously described and the concentration (Ci). Unsubscribed values are values measured based on the mass detector, LALLS, and areas of the viscometer. The value of K PE is iteratively adjusted, until the linear reference sample has a value measured in gpcBR of zero. For example, the final values for a and Log K for the determination of gpcBR in this specific case are 0.725 and -3.355, respectively, for polyethylene, and 0.722 and -3.933, respectively, for polystyrene.
    [0058] Considering that the K and α values were determined using the procedure discussed above, the procedure is repeated using the branched samples. Branched samples are analyzed using the final Mark-Houwink constants as the best cc calibration values, with Equations (2) - (9) being applied.
    [0059] The interpretation of gpcBR is straightforward. For linear polymers, the gpcBR calculated based on Equation (8) will be close to zero, since the values measured by LS and viscometer will be close to the conventional calibration standard. For branched polymers, gpcBR will be greater than zero, especially with high levels of long chain branching, since the measured polymer molecular weight will be greater than the calculated Mw, cc, and the calculated IVcc will be greater than the measured IV polymer. In fact, the gpcBR value represents a fractional IV change, due to the effect of molecular size contraction as a result of polymer branching. A gpcBR value of 0.5 or 2.0 would mean an IR molecular weight contraction effect at the level of 50% and 200%, respectively, versus a linear polymer molecule
    Petition 870190091036, of 9/13/2019, p. 35/57
    25/41 equivalent weight.
    [0060] For these specific examples, the advantage of using gpcBR, compared to a traditional g z index and branch frequency calculations, is the greater precision of gpcBR. All parameters used to determine the gpcBR index are obtained with good precision, and are not adversely affected by the low response of the 3DGPC detector to the high molecular weight of the concentration detector. Errors in the volume alignment of the detector also do not affect the accuracy of the gpcBR index determination.
    Film Test [0061] The following physical properties are measured on the films, as described in the experimental section.
    [0062] Total Opacity (Global) and Internal Opacity: Internal opacity and total opacity are measured according to ASTM D 1003-07. The internal opacity is obtained via homogeneity of the refractive index using mineral oil (1-2 teaspoons), applied as a coating on each surface of the film. A Hazegard Plus instrument (BYK-Gardner USA; Columbia, MD) is used for the test. For each test, five samples are examined and an average is reported. The sample dimensions were 6 inches x 6 inches.
    [0063] 45 ° brightness: ASTM D2457-08 (average of five film samples; each sample 10 inches x 10 inches).
    [0064] Transparency: ASTM D1746-09 (average of five samples; each sample 10 ”x 10”).
    [0065] 2% Secant Module - MD (machine direction) and CD (transversal direction): ASTM D882-10 (average of five film samples in each direction; each sample 1 in x 6 in).
    [0066] Tear resistance Elmendorf MD and CD: ASTM D1922
    Petition 870190091036, of 9/13/2019, p. 36/57
    26/41 (average of 15 film samples in each direction; each sample 3 inches x 2.5 inches in half moon shape).
    [0067] MD and CD Tensile Strength: ASTM D882-10 (average of five film samples in each direction; each sample 1 in. X 6 in.).
    [0068] Dart Drop Impact Resistance: ASTM D1709-09 (minimum of 20 drops to achieve 50% failure; typically 10 strips of 10 in x 36 in).
    [0069] Puncture resistance: drilling is measured on an instrument model 4201 by INSTRON with SOFTWARE SINTECH TESTWORKS version 3.10. The sample size is 6 inches x 6 inches, and four measurements are taken to determine the average drilling value. The film is conditioned for 40 hours after the film is produced, and for at least 24 hours in a controlled ASTM laboratory (23 ° C and 50% relative humidity). A 100 lbs load cell is used with a 4 inch diameter round sample holder. The drill rig is a polished stainless steel ball 1/2 inch in diameter (on a 2.5 inch rod) with a maximum travel length of 7.5.
    [0070] There is no useful length; the probe is as close as possible to the sample, without touching it, however (the probe is adjusted by raising it until it touches the sample). Then the probe is gradually lowered until it stops touching the sample. The traction speed is set to zero. Considering the maximum travel distance, the distance should be approximately 0.10. The traction speed is 10 / minute. The thickness is measured at the center of the sample. The thickness of the film, the distance traveled by the traction, and the peak load are used to determine the perforation through
    Petition 870190091036, of 9/13/2019, p. 37/57
    27/41 of the software. The drill rig is cleaned using a Kim-wipe cloth after each sample.
    [0071] Retraction stress: the retraction stress is measured according to the method described in Y.Jin, T.Hermel-Davidock, T.Karjala, M.Demirors, J.Wang, E.Leyva, and D.Allen , Shrink Force Measurement of Low Shrink Force Films, SPE ANTEC Proceedings, p.1264 (2008). The shrinkage stress of film samples is measured by means of a temperature ramp test conducted on a dynamic mechanical analysis instrument RSAIII (TA Instruments; New Castle, DE) with a film fastener. Film samples 12.7 mm wide and 63.5 mm long are cut in a matrix, in the machine direction (MD) or in the transverse direction (CD) to perform the test. The film thickness is measured by a Mitutoyo Absolute digital indicator (Model C112CEXB). This indicator has a maximum measurement range of 12.7mm with a resolution of 0.001mm. The average of three thickness measurements, in different locations of each film sample and in the sample width, is used to calculate the cross-sectional area of the film (A), where A = width x thickness of the film sample is used in the film test. retractable film. A standard TA Instruments film tension fixture is used for measurement. The RSA-III oven is equilibrated at 25 ° C for at least 30 minutes, before zeroing the gap and the axial force. The initial space is adjusted to 20 mm. The film sample is then attached to both the upper and lower fasteners. Typically, measurements for MD require one-layer film. Because the retraction voltage in the CD direction is typically low, two or more layers (layers) of films are stacked for each measurement in order to improve the signal / noise ratio. In that case, the
    Petition 870190091036, of 9/13/2019, p. 38/57
    28/41 film thickness is the sum of all layers. After the film reaches the initial temperature of 25 ° C, the upper fixator is manually raised or lowered slightly to obtain an axial force of -1.0g, thus avoiding excessive folding or stretching of the film at the beginning of the test. A constant space for the fixer is maintained throughout the measurement.
    [0072] The temperature ramp starts at a rate of 90 ° C / min, from 25 ° C to 80 ° C, followed by a rate of 20 ° C / min from 80 ° C to 160 ° C. During the ramp from 80 ° C to 160 ° C, as the film shrinks the retraction force, measured by the force transducer, it is registered as a function of the temperature for further analysis. The difference between the peak force and the baseline value before the start of the peak pullback force is considered to be the pullback force (F) of the film. The shrinkage stress of the film is the ratio of the shrinkage force (F) to the transverse area (A) of the film.
    EXPERIMENTAL [0073] The linear low density polyethylene, LLDPE1, used is produced by Ziegler Natta catalysis, with a melting index of 1 (I2 or MI), and 0.926 g / cm 3 of density, with Irgafos 168 additives of 1,000 ppm ( Ciba Specialty Chemicals, Inc., Basel, Switzerland).
    [0074] The examples are produced from that LLDPE1, extruded with different concentrations of additive derived from alkoxamine. The specific additive used is 9- (acetyloxy) -3,8,10-triethyl-7,8,10-trimethyl-1,5-dioxa-9azaspiro [5.5] undec-3-yl] methyl octadecanoate, which is added as a standard batch of LDPE, with 5,600 parts of additive per one million parts by weight of additive LDPE (note that the ppm levels reported below refer to the amount of
    Petition 870190091036, of 9/13/2019, p. 39/57
    29/41 added alkoxamine and not to the quantity of the entire standard batch added).
    [0075] The standard batch is prepared as described below. The alkoxamine-derived additive is combined with ethylene homopolymer resin prepared in a high pressure tubular reactor (ie an LDPE resin) with a melting index of 0.7g / 10 min (at 190 ° C, 2.16 kg , ASTM D1238) and a density of 0.925 g / cm3 (ASTM D792).
    [0076] The LDPE and the derivative are combined in a 30mm Coperion Werner-Pfleiderer ZSK-30 interpenetrating double screw extruder to form a standard batch. The ZSK-30 has ten barrel sections with a total length of 960 mm and a length / diameter (L / D) ratio of 32. A two-hole multi-wire die is used without a perforated plate or filter set. The extruder consists of a DC motor, connected to a gearbox via V-belts. The 15 Hp motor is driven through an adjustable GE variable speed drive located in a control box. The speed control range of the thread axis is 1:10 The maximum speed of the thread axis is 500 revolutions per minute. A pressure transducer is positioned in front of the matrix to measure the pressure of the matrix.
    [0077] The extruder has eight heated / cooled barrel sections together with a 30mm spacer, which constitute five temperature-controlled zones. It has only one section of chilled feed and only one section of heated matrix, held together by tie rods and supported on the machine structure. Each section can be heated electrically with concave angle heaters and cooled by a special system of cooling channels.
    Petition 870190091036, of 9/13/2019, p. 40/57
    30/41 [0078] The threads consist of continuous shafts on components with thread threads and special kneading elements are installed in any necessary order. The elements are held together radially by keys and keyways and axially by a threaded end. The screw shafts are connected to the gear shafts via couplings and can be easily removed from the screw barrel for disassembly.
    [0079] A Conair pelletizer is used to pellet the mixtures. It is a solid 220 volt variable speed cutting unit. The variable speed motor drives a solid machined cutting disc which in turn drives a fixed metal cylinder. A movable rubber cylinder compresses the fixed cylinder and helps to pull the friction filaments onto the cutting disc. The tension on the movable cylinder can be adjusted, if necessary.
    [0080] The temperatures are adjusted in the feed zone, 4 zones in the extruder, and in the matrix as follows: Feed80 ° C
    Zone 1160 ° C
    Zone 2180 ° C
    Zone 3185 ° C
    Zone 4190 ° C
    Matrix 210 ° C [0081] The thread spindle speed is set at 276 revolutions per minute (RPM), resulting in an output rate of 52 lbs / h.
    [0082] LLDPE1 and the standard batch of LLDPE / alkoxamine-derived additive are combined in a 30mm Coperion Werner interpenetrating double screw extruder
    Petition 870190091036, of 9/13/2019, p. 41/57
    31/41
    Pfleiderer ZSK-30 (ZSK-30). The ZSK-30 has ten barrel sections with a total length of 960 mm and a length / diameter (L / D) ratio of 32. A two-hole multi-wire die is used without a perforated plate or filter set. The extruder consists of a DC motor, connected to a gearbox via V-belts. The 15 Hp motor is driven through an adjustable GE variable speed drive located in a control box. The speed control range of the thread axis is 1:10 The maximum speed of the thread axis is 500 revolutions per minute. A pressure transducer is positioned in front of the matrix to measure the pressure of the matrix.
    [0083] The extruder has eight heated / cooled barrel sections together with a 30mm spacer, which constitute five temperature-controlled zones. It has only one section of chilled feed and only one section of heated matrix, held together by tie rods and supported on the machine structure. Each section can be heated electrically with concave angle heaters and cooled by a special system of cooling channels.
    [0084] The threads consist of continuous shafts on components with thread threads and special kneading elements are installed in any order necessary. The elements are held together radially by keys and keyways and axially by a threaded end. The screw shafts are connected to the gear shafts via couplings and can be easily removed from the screw barrel for disassembly.
    [0085] A Conair pelletizer is used to pellet the mixtures. It is a solid cutting unit of
    Petition 870190091036, of 9/13/2019, p. 42/57
    32/41 220 volt variable speed. The variable speed motor drives a solid machined cutting disc which in turn drives a fixed metal cylinder. A movable rubber cylinder compresses the fixed cylinder and helps to pull the friction filaments onto the cutting disc. The tension on the movable cylinder can be adjusted, if necessary.
    [0086] The temperatures are adjusted in the feed zone, 4 zones in the extruder, and in the matrix as follows: Feed80 ° C
    Zone 1160 ° C
    Zone 2180 ° C
    Zone 3185 ° C
    Zone 4190 ° C
    Matrix230 ° C [0087] The thread spindle speed is set at 325 revolutions per minute (RPM), resulting in an output rate of 40 lbs / h.
    [0088] LLDPE1 is extruded with the standard batch, so that 60ppm and 120 ppm of the alkoxamine-derived additive are added. LLDPE1 is also extruded separately. These three samples, together with the LLDPE before extrusion, are characterized with the results shown in Table 1. With the addition of the alkoxamine-derived additive, the melting index decreases, the melting index ratio (I10 / I2) increases, Viscosity increases, tan delta decreases, and melt strength increases compared to the initial LLDPE1 and extruded LLDPE1.
    Petition 870190091036, of 9/13/2019, p. 43/57
    33/41
    Table 1 - Melting indices, DMS viscosity, resistance of
    Cast and conventional calibration (cc) TDGPC data and gpcBR from LLDPE1, extruded LLDPE1, and LLDPE1 with 60 ppm and 120 ppm of alkoxamine-derived additive
    Comp example 4 Comp example 5 Example 2 Example 3LLDPE1 Extruded LLDPE1 Extruded LLDPE1 w / 60 ppm alkoxamine derivative additive Extruded LLDPE1 w / 120 ppm alkoxamine derived additive I2 (g / 10 min) 1, 09 0.90 0.66 0.44 I10 (g / 10 min) 8, 51 7, 67 0.45 5, 53 I10 / I2 7.83 8, 53 9.76 12.50 Visc. 0.1 rad / s(Pa-s) 7,982 10,525 14,633 25,838 Visc.1 rad / s (Pa-s) 6,359 7,324 9,004 12,292 Visc.10 rad / s (Pa-s) 3,906 4,093 4,539 4,993 Visc.100 rad / s (Pa-s) 1,600 1,609 1,686 1,680 Visc. 4.99 6, 54 8, 68 15, 38 Tan Delta 0, 1 rad / s 9, 09 4.98 3.39 2.01 Fused resistance(cN) 2, 7 3, 8 5, 6 7.3 cc-GPCMn (g / mol) 26,680 26,390 26,500 25,520 cc-GPCMw (g / mol) 106,380 106,780 109,390 102,950 cc-GPC Mz (g / mol) 319,700 316,000 335,100 290,500 cc-GPC Mw / Min 3.99 4.05 4, 13 4.03 gpcBR 0.015 0.069 0.01 0.068
    Visc = viscosity
    Viscosity ratio [0090] Based on the samples in Table 1, an additional sample is prepared for making a film compared to other comparative samples with an index of
    Petition 870190091036, of 9/13/2019, p. 44/57
    34/41 nominal fusion of 0.5 (I 2 = 0.5) in film for use in applications in retractable films for packaging unitization. In this case, 105 ppm of alkoxamine-derived additive is used.
    [0091] Three other comparative samples are used. Comparative Example 1 is an ethylene / octene LLDPE produced in accordance with US patent application No. 12 / 814,902 filed on June 14, 2010. Comparative Example 2 is an ethylene / octene LLDPE product according to the application international number PCT / US10 / 50745 deposited on September 29, 2010. Comparative Example 3 is produced from LLDPE1 and extrusion, as previously described, but using 355 ppm of bisulfonylazide diphenyl oxide (DPO-BSA) as an additive. This DPO-BSA is a mixture of DPO-BSA / Irganox I-1010 (Ciba Specialty Chemicals, Inc., Basel, Switzerland) in a ratio of 1 / 3.3.
    [0092] The characterization results of Example 1 and Comparative Examples 1-3 are shown in Table 2. The densities and I2 melt index of Example 1 and Comparative Examples 1-3 are comparable. The I10 / I2 viscosity ratio and the melt strength of Example 1 is the highest, indicating good processability.
    Petition 870190091036, of 9/13/2019, p. 45/57
    35/41
    Example1 Comp example 1 Comp example 2 Example comp.3 Density (g / cm 3 ) 0.9267 0.9289 0.9298 0.9266 I2 (g / 10 min) 0.59 0.46 0.56 0.67 I10 (g / 10 min) 6, 27 4.435 3.85 6, 31 I10 / I2 10, 59 9, 6 6, 91 9.41 Visc. 0.1 rad / s (Pa-s) 19,074 22973.9 12,096 16,919 Visc.1 rad / s (Pa-s) 10,515 12214.3 9, 823 9, 353 Visc.10 rad / s (Pa-s) 4, 826 5774.54 5, 852 4,580 Visc.100 rad / s (Pa-s) 1. 708 2148.41 2,217 1,689 Visc. 11, 17 10, 69 5.46 10, 02 Tan Delta 0.1 rad / s 2.64 2.80083 10, 18 2.57 Fused resistance (cN) 7.2 5, 8 4.3 6, 7 cc-GPC Mn (g / mol) 25,980 35240 36,720 27,390 cc-GPC Mw (g / mol) 109,960 101610 137,000 117,350 cc-GPC Mz (g / mol) 329,700 217500 355,500 377,900 cc-GPC Mw / Min 4.23 2.88 3.73 4.28 gpcBR 0.098 0.070 0. 166 0. 104
    Vise = viscosity
    Viscosity ratio [0094] Monolayer blown films are prepared from the samples in Table 2. Monolayer films are also prepared in a composition of 65% by weight of LLDPE (samples in Table 2) and 35% by weight of LDPE in which the LDPE used is a high pressure, low density polyethylene manufactured by The Dow Chemical Company (LDPE 1321, 0.25 MI, 0.921 g / cm 3 ). For LLDPE / LDPE mixture samples, appropriate amounts are measured using a laboratory scale. Then, the mixed compound, in a large bag with sufficient space, is stirred manually for two minutes until the mixture is homogeneous. This technique is generally referred to as the mixed dry mix technique (salt and pepper).
    [0095] Monolayer blown films are prepared in multiple extruders (25mm (E25P x 25 L / D), 30mm (E30P x 25
    Petition 870190091036, of 9/13/2019, p. 46/57
    36/41
    L / D) and 25mm (E25P x 25 L / D)) manufactured by Dr. Collin. Each extruder has a gravimetric feed system that calculates the exit rate. Each extruder has a standard monofilament feed thread.
    [0096] The opening of the matrix for all films is 2mm and the blowing ratio (BUR) 2.5. The process conditions for the 100% LLDPE samples from Table 2 are shown in Table 3. The process conditions for the 65% LLDPE samples with 35% LDPE 1321 are shown in Table 4.
    Table 3: Process conditions for blown films prepared according to Example 1 and Comparative Examples 1-3
    Sample Example1 Example comp.1 Example comp.2 Example comp.3 Target film thickness (mil) 1 1 1 1 Cast in extruder T (° C) 185 186 186 185 Yield inside extruder (kg / h) 1, 9 1, 9 1, 9 1, 9 RPM in the extruder 45 45 45 45 Cast Extruder CoreT (° C) 183 185 182 185 Core inside extruder (kg / h) 2 1, 9 1, 9 2 Core in the RPM extruder 25 25 25 25 Cast out T extruder (° C) 187 187 185 185 Core outside extruder (kg / h) 1, 8 1, 9 1, 9 1, 9 RPM outside extruder 45 45 45 45 Starting speed (m / min) 8, 4 8, 4 8, 4 8, 4 Blower (%) 46 46 46 43 Useful width (cm) 23, 25 23, 25 23, 25 23, 5 Freezing level (inches) 4 4 4 4 Total yield (kg / h) 5, 7 5, 7 5, 7 5, 8
    Petition 870190091036, of 9/13/2019, p. 47/57
    37/41
    Table 4: Process conditions for blown films prepared with 65% of the samples in Table 2 and 35% of LDPE 132I.
    Sample 65%Example 1/35% LDPE 132I 65% Example comp. 1/35% LDPE 132I 65% Example comp. 3/35% LDPE 132I Target film thickness (mil) 1.5 1.5 1.5 Cast in extruder T (° C) 185 186 185 Yield within extruder(kg / h) 2.4 2.5 2.5 RPM inside extruder 60 60 60 Cast extruder core T (° C) 185 183 184 Core inside extruder (kg / h) 2, 6 2, 6 2, 6 Extruder core RPM 35 35 35 Cast out T extruder (° C) 187 187 200 Core outside extruder (kg / h) 2.5 2.5 2, 6 RPM outside extruder 60 60 60 Starting speed (m / min) 7.8 8 7.8 Blower (%) 61 61 59 Useful width (cm) 23 23 23, 5 Freezing level (inches) 3 3 3 Total yield (kg / h) 7.5 7, 6 7.7
    [0097] The properties of the films are measured, with results shown in Table 5 for 100% LLDPE films and in Table 6 for 65% / 35% LDPE films. For the 100% LLDPE films in Table 5, Example 1 shows relatively good optical properties (high transparency, high gloss, and low opacity), similar to LLDPE resins not produced by extrusion with additives, such as Comparative Example 1 and Comparative Example 2. Comparative Example 3, produced by extrusion with an additive different from that of Example 1, shows very poor optical properties. Other advantages of Example 1 are the high resistance to tearing MD and CD, good resistance to impact by
    Petition 870190091036, of 9/13/2019, p. 48/57
    38/41 dart drop, and good puncture resistance. Example 1 shows the highest MD shrinkage stress and a high CD shrinkage stress, indicating that this resin and film could be beneficial in shrinkable film applications. The films prepared with Example 1 show a good drying module, also important for shrink film applications.
    [0098] Table 6 shows similar conclusions for LLDPE 65% / LDPE 1321 35% films, as seen in 100% films. Example 1 has relatively good optical properties (high transparency, high gloss and low opacity), similar to those observed for LLDPE resins not produced by extrusion with additives, such as Comparative Example 1 and Comparative Example 2. The film prepared with Example 1 has the lowest internal opacity. The film prepared with Comparative Example 3, produced by extrusion with an additive different from that of Example 1, shows very poor optical properties. Other advantages of the film prepared with Example 1 are the high resistance to tearing MD and CD, good resistance to impact by dart drop, and good resistance to perforation. The film prepared with Example 1 shows the highest MD shrinkage stress and a high CD shrinkage stress, indicating that this resin and film could be beneficial in shrinkable film applications. The films prepared with Example 1 also show a good drying module, important for shrink film applications.
    [0099] For the films in Table 5, the MD shrinkage stress was determined using 1 film layer and the CD shrinkage stress was determined using 4 film layers. For the films in Table 6, the MD shrinkage stress was determined using 1 film layer and the
    Petition 870190091036, of 9/13/2019, p. 49/57
    39/41 CD retraction was determined using 2 layers of film.
    Table 5: Film properties for blown films prepared with Example 1 and Comparative Examples 1-3
    Example1 100% Comp example 1 100% Comp example 2 100% Example comp. 100% Thickness (mil) 1.01 0.95 0.94 0.95 Density (g / cm 3 ) 0.9264 0.9284 0.9274 0.9269 I2 0.33 0.48 0.54 0.53 I10 4.67 4.43 3.80 5.66 I10 / I2 14.32 9, 17 7.03 10, 64 Total opacity (%) 13, 6 12.2 5, 5 35, 3 Total internal opacity (%) 2.7 2.8 2.0 5, 8 45 ° brightness (%) 42, 9 48, 3 72.0 15, 5 Transparency (%) 95, 7 98, 6 99.5 52, 9 Tear B CD (g) 708 537 523 545 Tear B MD (g) 204 143 243 144 Dart A (g) 133 73 160 133 Perforation (pelibra / square inch) 150 188 293 124 Drying module 2% -CD (psi) 38,993 41,846 43,918 42,246 Drying module 2% -MD (psi) 38,548 41,303 42,935 40,953 Breaking stress CD (psi) 5.361 5, 624 7, 111 4.835 Deformation at CD rupture (%) 613 618 619 578 Deformation in the CD flow 7 8 7 7 Limiting stress in the DC flow (Psi) 2. 146 2,463 2,370 2,338 Breakdown voltage MD (Psi) 6, 082 6, 313 5.361 4,495 Deformation at break MD (%) 430 483 436 454 Deformation in the CD flow 7 9 8 7 Limiting stress in flow MD (Psi) 2,014 2.307 2. 161 2,086 Retraction voltage MD (Psi) 16, 95 10, 43 6, 94 12.81 Standard deviation, CD retraction stress (Psi) 1.73 1, 57 1, 12 0.97 Retraction stress CD (Psi) 0.71 0.71 0.82 0.72 Standard deviation Retraction voltage MD (Psi) 0.15 0.16 0.33 0.39
    Petition 870190091036, of 9/13/2019, p. 50/57
    40/41
    Table 6: Film properties for blown films prepared with 65% of the samples in Table 2 and 35% LDPE 1321.
    Example1 100% Comp example 1 100% Example comp.2 100% Thickness (mil) 1.46 1.44 1.41 Density (g / cm 3 ) 0.92 0.93 0.92 I2 0, 24 0.31 0.33 I10 3.72 3.53 4.29 I10 / I2 15.41 11, 45 13, 20 Total opacity (%) 12, 1 9, 8 22.7 Total internal opacity (%) 3.0 3, 5 9, 0 45 ° brightness (%) 45, 5 51.5 27.4 Transparency (%) 89, 8 94.4 74.8 Tear B CD (g) 778 692 739 Tear B MD (g) 131 81 104 Dart A (g) 115 88 124 Drilling(foot-pounds / square inch) 128 160 113 Drying module 2% -CD (psi) 40,723 44,262 41,461 Drying module 2% -MD (psi) 34,931 40,005 36,128 Breaking stress CD (psi) 4.725 5.032 5.021 Deformation at CD rupture (%) 634 665 650 Deformation in the CD flow 8 8 8 Limiting voltage in the flow. CD (Psi) 2,073 2.306 2,080 Breakdown voltage MD (Psi) 4,395 4.855 4,321 Deformation at break MD (%) 338 401 376 Deformation in the CD flow 7 7 8 Limiting voltage in the flow. MD (Psi) 1.858 2,063 1,882 Retraction voltage MD (Psi) 24.79 19, 56 19, 43 Standard deviation, CD retraction stress (Psi) , 44 0.96 19, 54 Retraction stress CD (Psi) 0.53 0.86 0.39 Standard deviation Retraction voltage MD (Psi) 0.09 0.14 0.49
    [0100] Although the present invention has been described in considerable detail in the description and previous examples, such details are for illustration only and should not be construed as restricting the scope of the invention, described in the appended claims. All patents, published patent applications and patent applications granted
    Petition 870190091036, of 9/13/2019, p. 51/57
    41/41 identified above are hereby incorporated by reference.
    权利要求:
    Claims (4)
    [1]
    1. Method to produce film, said method being characterized by the fact of understanding the steps of:
    a) mixing an alkoxyamine derivative with a low density polyethylene to form a masterbatch;
    b) select a target polyethylene resin having a density, as determined according to ASTM D792, in the range of 0.92 g / cm3 to 0.94 g / cm3, and a melting index, as determined according to ASTM D1238 (2.16 kg, 190 ° C) in the range of 0.01 g / 10 min to 10 g / 10 min; wherein the target polyethylene is a low density polyethylene;
    c) mix the masterbatch with the target polyethylene in an amount and under sufficient conditions to increase the
    resistance to the cast gives resin of polyethylene; where the amount of derivative in alkoxy amine is lower to 900 parts by million with weight basis total resin polyethylene ; and d) mix the composition in (c) with 10 to 90 percent by weight
    in an composition in low polyethylene density for to form a mix (d) containing the derivative of alkoxiamine in an amount of 1 at 400 ppm; and
    e) form a film from the mixture (d).
    [2]
    2. Method, according to claim 1, characterized by the fact that the alkoxamine derivative corresponds to the formula:
    (R1) (R2) NO-R3 where R1 and R2 are each independently hydrogen, C4-C42 alkyl or C4-C42 aryl or substituted hydrocarbon groups comprising O and / or N, and where R1 and R2 can form together a ring structure; and where R3 is
    Petition 870190091036, of 9/13/2019, p. 53/57
    2/4 hydrogen, a hydrocarbon or hydrocarbon group
    substituted3. Method, comprising O and / or N. featured in a deal with The claim 1, by the fact in the derivative in alkoxiamine to be an ester of hydroxylamine. 4. Method, in a deal with The claim 3, featured by the fact that hydroxylamine ester be 9- octadecanoate
    (acetyloxy) -3,8,10-triethyl-7,8,10-trimethyl-1,5-dioxa-9azaspiro [5.5] undec-3-yl] methyl.
    5. Method, according to claim 1, characterized in that the resulting film is a retractable film.
    6. Film, characterized by the fact of understanding:
    a) 10 to 90 weight percent of a polyethylene polymer, prepared by the process of:
    i) select a target polyethylene resin with a density, determined according to ASTM D792, in the range of 0.90 g / cm 3 to 0.955 g / cm 3 , and a melting index, determined according to ASTM D1238 (2 , 16 kg, 190 ° C) in the range of 0.01 g / 10 min to 10 g / 10 min; wherein the target polyethylene is a linear low density polyethylene;
    ii) mixing an alkoxyamine derivative with a low density polyethylene to form a masterbatch;
    iii) mixing the masterbatch with a target polyethylene in an amount and under conditions sufficient to increase the melt strength of the polyethylene resin, the amount of the alkoxyamine derivative being less than 900 parts per million based on the total weight of the polyethylene resin. polyethylene; and
    b) add from 10 to 90 weight percent of a low density polyethylene composition to a mixture obtained in
    Petition 870190091036, of 9/13/2019, p. 54/57
    [3]
    3/4 (iii) to form a composition containing the alkoxyamine derivative in an amount of 1 to 400 ppm.
    7. Film according to claim 6, characterized in that said target polyethylene has a density in the range of 0.920 to 0.935 g / cm 3 .
    8. Film, according to claim 6, characterized by the fact that said target polyethylene has a melting index in the range of 0.01 to 3g / 10 minutes.
    9. Film according to claim 6, characterized in that said target polyethylene has a molecular weight distribution, M w / M n , less than 5.
    10. Film, according to claim 6, characterized by the fact that it has an MD retraction voltage greater than 20 cN and an opacity less than 15%.
    11. Film, according to claim 6, characterized by the fact that it has an MD tear resistance greater than 100g and a CD tear resistance greater than 700g.
    12. Film, according to claim 6, characterized in that the melt flow ratio of I10 / I2 of the target polyethylene is greater than 9.
    13. Film according to claim 6, characterized in that the [Viscosity at 0.1 rad / s] / [Viscosity at 100 rad / s] of the target polyethylene measured at 190 ° C is greater than 8.
    14. Film, according to claim 6, characterized by the fact that the tan delta of 0.1 rad / s of the target polyethylene, measured at 190 ° C, is less than 4.
    15. Film according to claim 6, characterized in that the melt strength of the target polyethylene measured as the plateau strength (cN) at 190 ° C is greater than 5.
    16. Film according to claim 6, characterized
    Petition 870190091036, of 9/13/2019, p. 55/57
    [4]
    4/4 because the gpcBR of the target polyethylene is greater than 0.03.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112012017118B1|2019-11-19|method to produce film and film
    JP2017101251A|2017-06-08|Ethylene polymer and manufacturing method therefor
    BR112015006812B1|2021-03-23|COMPOSITION
    BR112014031191B1|2021-08-24|POLYETHYLENE MIXTURE COMPOSITION SUITABLE FOR BLOW FILM AND BLOW FILM
    ES2702346T3|2019-02-28|Ethylene-based polymers and processes for producing them
    BR112014025322B1|2021-06-01|POLYETHYLENE MIXTURE-COMPOSITION, BLOW FILM, CONTAINER ARTICLE AND DEVICE
    BR112014000321B1|2020-11-03|mix composition of polyethylene, blown film, article and container device
    EP2729523B1|2015-09-16|Ethylene-based polymers compositions
    同族专利:
    公开号 | 公开日
    RU2012134354A|2014-02-20|
    CN102782021B|2015-10-07|
    AR079988A1|2012-03-07|
    MX347015B|2017-04-07|
    KR101835646B1|2018-03-08|
    KR101802542B1|2017-11-28|
    CN102939325B|2015-08-19|
    EP2523980A1|2012-11-21|
    RU2012134319A|2014-02-20|
    MX355569B|2018-04-23|
    JP2013516546A|2013-05-13|
    KR20120120207A|2012-11-01|
    JP5877794B2|2016-03-08|
    JP5735540B2|2015-06-17|
    CN102782021A|2012-11-14|
    CN102892789A|2013-01-23|
    US20130035444A1|2013-02-07|
    KR20120123310A|2012-11-08|
    US8653196B2|2014-02-18|
    MX2012008099A|2013-01-29|
    US8987382B2|2015-03-24|
    JP2013516545A|2013-05-13|
    SG182358A1|2012-08-30|
    KR101886701B1|2018-08-10|
    US9422425B2|2016-08-23|
    RU2012134431A|2014-02-20|
    BR112012016643A2|2016-05-03|
    US20130022804A1|2013-01-24|
    MX2012008102A|2013-02-12|
    US20130035438A1|2013-02-07|
    CN102892789B|2016-01-20|
    JP5643843B2|2014-12-17|
    WO2011085375A1|2011-07-14|
    JP2013516543A|2013-05-13|
    BR112012016645A2|2016-05-03|
    JP5973919B2|2016-08-23|
    AR079986A1|2012-03-07|
    SG182356A1|2012-08-30|
    MX2012008101A|2013-02-12|
    SG182357A1|2012-08-30|
    US20120283390A1|2012-11-08|
    MX2012008100A|2013-02-12|
    RU2012134320A|2014-02-20|
    MY169967A|2019-06-19|
    US20110171407A1|2011-07-14|
    MX342618B|2016-10-06|
    US8664337B2|2014-03-04|
    EP2523981A1|2012-11-21|
    WO2011085371A1|2011-07-14|
    MX347084B|2017-04-11|
    SG182359A1|2012-08-30|
    BR112012017118A2|2017-06-20|
    CN102985448A|2013-03-20|
    AR079989A1|2012-03-07|
    EP2523991A1|2012-11-21|
    BR112012016745A2|2017-06-13|
    AR079987A1|2012-03-07|
    SG10201500173UA|2015-03-30|
    CN102985448B|2016-01-20|
    KR20120116432A|2012-10-22|
    KR20120123312A|2012-11-08|
    WO2011085377A1|2011-07-14|
    WO2011085379A1|2011-07-14|
    JP2013516544A|2013-05-13|
    CN102939325A|2013-02-20|
    EP2523992A1|2012-11-21|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3709853A|1971-04-29|1973-01-09|Union Carbide Corp|Polymerization of ethylene using supported bis-chromiumcatalysts|
    US4339507A|1980-11-26|1982-07-13|Union Carbide Corporation|Linear low density ethylene hydrocarbon copolymer containing composition for extrusion coating|
    US4409367A|1981-01-20|1983-10-11|Akzona Incorporated|Process for cross-linking polymers|
    JPS64985B2|1981-08-14|1989-01-10|Asahi Chemical Ind|
    JPS6242922B2|1982-05-11|1987-09-10|Asahi Chemical Ind|
    US4603173A|1985-02-27|1986-07-29|E. I. Du Pont De Nemours And Company|Processing polyethylene resins|
    DE3851667T2|1987-07-13|1995-02-16|Mitsubishi Chem Ind|Linear polyethylene film and process for its manufacture.|
    US5525695A|1991-10-15|1996-06-11|The Dow Chemical Company|Elastic linear interpolymers|
    SE9103077D0|1991-10-22|1991-10-22|Neste Oy|UNSATURED FOOD COPY POLYMER AND SET FOR PREPARATION THEREOF|
    US6143854A|1993-08-06|2000-11-07|Exxon Chemical Patents, Inc.|Polymerization catalysts, their production and use|
    US6545088B1|1991-12-30|2003-04-08|Dow Global Technologies Inc.|Metallocene-catalyzed process for the manufacture of EP and EPDM polymers|
    DE69211569T2|1991-12-30|1997-01-23|Dow Chemical Co|ETHYLENE INTERPOLYMER POLYMERIZATION|
    US6448341B1|1993-01-29|2002-09-10|The Dow Chemical Company|Ethylene interpolymer blend compositions|
    BR9405715A|1993-01-29|1995-11-28|Dow Chemical Co|Process for preparing an ethylene / a-olefin interpolymer composition and ethylene / a-olefin interpolymer composition|
    US5486575A|1994-03-08|1996-01-23|Quantum Chemical Corporation|High performance blow molding resins and process for their preparation|
    US5869575A|1995-08-02|1999-02-09|The Dow Chemical Company|Ethylene interpolymerizations|
    JPH11310612A|1998-04-30|1999-11-09|Mitsubishi Chemical Corp|Polymer having ethylenic linkage, and production and use thereof|
    CA2296306C|1999-01-21|2003-09-23|Mima Films S.C.A.|Low-noise stretch film|
    FR2805268B1|2000-02-23|2005-03-25|Atofina|THERMOREVERSIBLE POLYMERS WITH MITROXIDE FUNCTIONS|
    US7030196B2|2000-05-19|2006-04-18|Ciba Specialty Chemicals Corporation|Process for reducing the molecular weight of polypropylene|
    DK1282630T3|2000-05-19|2006-09-04|Ciba Sc Holding Ag|Process for reducing the molecular weight of polypropylene using hydroxylamine esters|
    US20050197433A1|2000-05-30|2005-09-08|Michael Roth|Molecular weight modification of thermoplastic polymers|
    JP5042435B2|2000-05-30|2012-10-03|チバホールディングインコーポレーテッド|Molecular weight control of thermoplastic polymers|
    DE60141754D1|2000-07-28|2010-05-20|Westlake Longview Corp|POLYETHYLENE COMPOSITIONS AND FOILS WITH IMPROVED VAPOR PERMEABILITY|
    US6433103B1|2001-01-31|2002-08-13|Fina Technology, Inc.|Method of producing polyethylene resins for use in blow molding|
    US6984698B2|2001-01-31|2006-01-10|Fina Technology, Inc.|Polyethylene films for barrier applications|
    WO2002092653A1|2001-05-15|2002-11-21|Ciba Speciality Chemicals Holding Inc.|Method of grafting ethylenically unsaturated carboxylic acid derivatives onto thermoplastic polymers using hydroxylamine esters|
    US6930137B2|2002-05-31|2005-08-16|Fina Technology, Inc.|Method of improving blown film processing performance and physical properties|
    EP1858971B1|2005-03-17|2019-04-24|Dow Global Technologies LLC|Rheology modification of interpolymers of ethylene/alpha-olefins and articles made therefrom|
    US20100210800A1|2004-03-24|2010-08-19|Ciba Corporation|Method of preparing ethylene polymers by controlled high pressure polymerization|
    EP1727837B1|2004-03-24|2007-12-12|Ciba Specialty Chemicals Holding Inc.|Method of preparing ethylene polymers by controlled high pressure polymerization|
    US7183005B2|2004-08-20|2007-02-27|Exxonmobil Chemical Patents Inc.|Impact strength improvement of regrind|
    RU2415206C2|2005-08-19|2011-03-27|Дау Глобал Текнолоджиз, Инк.|Layers of nonwoven material made by blowing propylene-based polymer melt, and composite structures|
    JP5055805B2|2005-09-30|2012-10-24|住友化学株式会社|Ethylene-α-olefin copolymer, resin composition and film|
    US7238754B1|2005-12-12|2007-07-03|Equistar Chemicals, Lp|Solid state process to modify the melt characteristics of polyethylene resins and products|
    US20090209158A1|2006-04-26|2009-08-20|Richeson Galen C|Pelletized Polymer Product And Process For Making The Same|
    US7816478B2|2008-09-03|2010-10-19|Equistar Chemicals, Lp|Polyethylene thick film and process for preparing polyethylene|
    US20110003940A1|2009-07-01|2011-01-06|Dow Global Technologies Inc.|Ethylene-based polymer compositions for use as a blend component in shrinkage film applications|
    US8653196B2|2010-01-11|2014-02-18|Dow Global Technologies, Llc|Method for preparing polyethylene with high melt strength|US8653196B2|2010-01-11|2014-02-18|Dow Global Technologies, Llc|Method for preparing polyethylene with high melt strength|
    US9428636B2|2011-03-28|2016-08-30|Dow Global Technologies Llc|Process to produce enhanced melt strength ethylene/α-olefin copolymers and articles thereof|
    WO2013006409A1|2011-07-06|2013-01-10|Dow Global Technologies Llc|Polyethylene with high melt strength for use in extrusion coating|
    US20140148535A1|2011-07-07|2014-05-29|Dow Brasil Indústria e Comércio de Produtos Químicos Ltda.|Ethylene-based polymers compositions|
    ES2587441T3|2011-08-26|2016-10-24|Dow Global Technologies Llc|Bioriented polyethylene film|
    US20160272798A1|2011-09-23|2016-09-22|Exxonmobil Chemical Patents Inc.|Modified Polyethylene Compositions with Enhanced Melt Strength|
    US9321911B2|2011-09-23|2016-04-26|Exxonmobil Chemical Patents Inc.|Modified polyethylene compositions for cast film|
    US9340664B2|2011-09-23|2016-05-17|Exxonmobil Chemical Patents Inc.|Modified polyethylene compositions for blown film|
    US20140072787A1|2012-09-13|2014-03-13|Dow Brasil S.A.|Polyolefin based films suitable for thermoforming|
    IN2015DN02921A|2012-09-28|2015-09-18|Dow Global Technologies Llc|
    EP3225639B1|2013-03-28|2019-12-18|Dow Global Technologies LLC|An ethylene/alpha-olefin interpolymer|
    JP6405366B2|2013-05-02|2018-10-17|ダウ グローバル テクノロジーズ エルエルシー|Polyethylene composition and articles made therefrom|
    US9346897B2†|2013-05-14|2016-05-24|Chevron Phillips Chemical Company Lp|Peroxide treated metallocene-based polyolefins with improved melt strength|
    CA2955941A1|2014-07-25|2016-01-28|Dow Global Technologies Llc|A polyethylene blend composition and film made therefrom|
    US10336893B2|2014-12-23|2019-07-02|Dow Global Technologies Llc|Process for preparing a modified ethylene-based polymer using a hydrocarbon initiator|
    JP6785799B2|2015-06-30|2020-11-18|ダウ グローバル テクノロジーズ エルエルシー|Polyethylene film with matte surface|
    KR101924198B1|2015-12-23|2018-11-30|주식회사 엘지화학|Low density polyethylene copolymer having superior film processibility and transmittance|
    JP6932713B2|2016-03-31|2021-09-08|ダウ グローバル テクノロジーズ エルエルシー|Modified polyethylene resin and method for producing it|
    EP3238938A1|2016-04-29|2017-11-01|Borealis AG|Machine direction oriented films comprising multimodal copolymer of ethylene and at least two alpha-olefin comonomers|
    CN107880193A|2016-09-29|2018-04-06|中国石油化工股份有限公司|A kind of preparation method of the high melting means LDPE PP Pipe Compounds of PUR|
    US11193008B2|2017-04-10|2021-12-07|Exxonmobil Chemical Patents Inc.|Methods for making polyolefin polymer compositions|
    US10858504B2|2017-07-06|2020-12-08|Exxonmobil Chemical Patents Inc.|Polyethylene compositions comprising cyclic-olefin copolymers|
    CA3076592A1|2017-09-27|2019-04-04|Dow Global Technologies Llc|Modified polyethylene compositions and method for making the same|
    US11177536B2|2017-11-08|2021-11-16|Lg Chem, Ltd.|Separator with reduced ignition phenomenon upon battery perforation and battery including the same|
    CN109827922B|2019-03-20|2021-08-13|深圳市艾科尔特检测有限公司|Correction method for copper ion interference during determination of nitrate nitrogen in water polluted by copper ions|
    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-07-16| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2019-10-15| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2019-11-19| 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 11/01/2011, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 11/01/2011, OBSERVADAS AS CONDICOES LEGAIS |
    2021-11-03| B21F| Lapse acc. art. 78, item iv - on non-payment of the annual fees in time|Free format text: REFERENTE A 11A ANUIDADE. |
    2022-02-22| B24J| Lapse because of non-payment of annual fees (definitively: art 78 iv lpi, resolution 113/2013 art. 12)|Free format text: EM VIRTUDE DA EXTINCAO PUBLICADA NA RPI 2652 DE 03-11-2021 E CONSIDERANDO AUSENCIA DE MANIFESTACAO DENTRO DOS PRAZOS LEGAIS, INFORMO QUE CABE SER MANTIDA A EXTINCAO DA PATENTE E SEUS CERTIFICADOS, CONFORME O DISPOSTO NO ARTIGO 12, DA RESOLUCAO 113/2013. |
    优先权:
    申请号 | 申请日 | 专利标题
    US12/685,148|US8653196B2|2010-01-11|2010-01-11|Method for preparing polyethylene with high melt strength|
    PCT/US2011/020846|WO2011085375A1|2010-01-11|2011-01-11|Polyethylene with high melt strength for use in films|
    [返回顶部]