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    • 专利摘要:
    POLYMER BASED ON ETHYLENE, COMPOSITION AND FILM LAYER An ethylene-based polymer characterized by having a density of about 0.9 to about 0.94 grams per cubic centimeter, a molecular weight distribution (Mw / Mn ) from about 4 to about 10, a melt index (12) of about 0.05 to about 2 grams for 10 minutes, a gpcBR value greater than 0.05 as determined by a gpcBR branch index and a Y value greater than 0.4. This ethylene-based polymer is especially useful for mixing with other polymers such as LLDPE. When the mixture is converted into film, especially in a retractable film, the film shows good optics, good shrinkage tension, high rigidity, high stress modulus, and stress resistance. When this resin is mixed with an LLDPE in a film blowing line, improvements are seen in the opacity ("haze"), brightness, transparency, and tearing ("tear") MD and CD, when compared to a comparative LDPE.
    公开号:BR112012003072B1
    申请号:R112012003072-8
    申请日:2010-08-04
    公开日:2020-11-17
    发明作者:Teresa P. Karjala；Colleen M. Tice；Jose Ortega；Lori L. Kardos；Wallace W. Yau；Jian Wang
    申请人:Dow Global Technologies Llc；
    IPC主号:
    专利说明:

    Background of the invention
    [001] There are many types of polyethylene made and sold today. A particular type is made by several suppliers and sold in large quantities. This polyethylene is called low density polyethylene with high pressure free radical (usually called LDPE) and is normally produced using a tubular reactor or an autoclave reactor or, sometimes, a combination of these. Sometimes, polymer users mix LDPE with other polymers, such as linear low density polyethylene (LLDPE) to try to modify properties, such as flowability or processability.
    [002] New LDPE polymers have been discovered, which especially when mixed with LLDPE, can have an improved shrinkage in combination with favorable stiffness, tensile strength, melt resistance and optics, while maintaining other performance attributes. Summary of the invention
    [003] In one embodiment, the invention is an ethylene-based polymer, preferably a homopolymer or copolymer, characterized by having a density of about 0.9 to about 0.94 grams per cubic centimeter, a distribution of molecular weight (Mw / Mn) of about 4 to about 10, preferably about 4 to about 6, a melt index (I2) of about 0.05 to about 2 grams for 10 minutes, preferably less than 0.8, more preferably, less than 0.5 grams / 10 minutes, a gpcBR value greater than 0.05 as determined by the gpcBR branching index and a GPC-LS characterization Y value greater than about 0.4, preferably, greater than about 0.5. Preferably, the ethylene-based polymer has a melt strength at 190 ° C in cN greater than 9 cN. At least one layer of film ("film layer") comprising the polymer based on ethylene can be made, especially, where the film layer has a retraction tension (MD) in the machine direction greater than 82.7 kPa (12 psi).
    [004] Preferably, the ethylene-based polymer has a cc-GPC MW in g / mol and a shear viscosity ratio of zero (η0) (Pa * s) log (η0 (Pa * s at 190 ° C)) > 12,333 * log (ccGPC MW in g / mol) - 56,367, especially where the melt index of the ethylene-based polymer is less than 0.7 grams / 10 minutes, preferably the log (ccGPC Mw in g / mol) is greater than 4.88.
    [005] The ethylene-based polymer can be used in a composition comprising the ethylene-based polymer and at least one other natural or synthetic polymer, especially where the synthetic polymer is selected from the group consisting of a linear low density polyethylene (LLDPE), a high density polyethylene (HDPE), and a low density polyethylene (LDPE), preferably, where the synthetic polymer comprises LLDPE, more preferably, where the LLDPE comprises less than 50 weight percent of the composition.
    [006] At least one film layer comprising the composition made using the ethylene-based polymer can be made. Brief description of the drawings
    [007] Figure 1 illustrates a diagram of a process describing the elements of a reactor system in tubes 100;
    [008] Figure 2 illustrates the profile of a light permeation gel permeation chromatography (LS-GPC) with a positive Al type area segment;
    [009] Figure 3 illustrates the profile of a gel permeation chromatography by light scattering (LS-GPC) with an A2 type negative area segment;
    [010] Figure 4 illustrates the profile of a gel permeation chromatography by light scattering (LS-GPC) with both segments of areas of the positive type Al and of the negative type A2;
    [011] Figure 5 illustrates a schematic of the process used to make the examples of that invention;
    [012] Figure 6 shows a diagram of the temperature and reaction zone in the process used to prepare Example 1;
    [013] Figure 7 illustrates a GPC-LS characterization value (Y) versus the molecular weight distribution through conventional TDGC calibration for the examples of this invention and the comparative examples;
    [014] Figure 8 illustrates the log of the zero shear viscosity versus the average molecular weight of the weight through conventional TDGPC calibration for the examples of this invention and comparative examples;
    [015] Figure 9 illustrates the total opacity of the blown films from mixture 1 to mixture 4;
    [016] Figure 10 shows a degree of brightness 45 and the transparency of the blown films of mixture 1 to mixture 4; and
    [017] Figure 11 illustrates the break in the machine direction (MD) and in the transversal direction (CD) of mixture 1 to mixture 4. Detailed description of the invention
    [018] An LDPE (low density polyethylene) resin that would allow the conversion of the film to improve the shrinkage of the films from their blowing / insufflation lines when mixed with 5 to 90% (based on weight) of an LLDPE resin ( linear low density polyethylene) with general retention of mechanical properties would be useful.
    [019] Using tubular high pressure LDPE technology, a resin is developed with a relatively limited molecular weight distribution (MWD). This resin when inflated in film demonstrates good optics, good shrinkage tension, high rigidity, high stress modulus, and stress resistance. When this resin is mixed at 80% (by weight) with an LLDPE in a film blowing / insufflation line, improvements are observed in opacity, brightness, transparency, and breakage in MD and CD, when compared to a comparative LDPE.
    [020] The melting index of the ethylene-based polymer LDPE is from about 0.05 to about 50 g / 10 minutes, preferably from about 0.05 to about 2 g / 10 minutes. The density of the LDPE ethylene-based polymer is from about 0.9 to about 0.94 g / cm3, preferably from about 0.923 to about 0.935 g / cm3. The ethylene-based polymer LDPE can have a melt strength of about 9 to about 40 cN. LDPE ethylene-based polymers have an MWD (Mw / Mn) of about 4 to about 10, a Y value of about 0.4 to about 10, and an MD retraction stress of about 10 to 40 cN.
    [021] The low density ethylene-based polymer can be an ethylene homopolymer. The low density ethylene-based polymer can be an ethylene-based interpolymer, comprising ethylene and at least one comonomer. Comonomers useful for incorporation into an ethylene-based interpolymer, especially an ethylene / a-olefin interpolymer include, but are not limited to, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, and mixtures of the themselves. Ethylene is often copolymerized with at least one C3-C20 α-olefin such as propene, 1-butene, 1-hexene and 1-octene.
    [022] A low density ethylene based polymer is described, which has a relationship between the response value of the concentration-normalized (LS) light spread and the molecular weight distribution as determined by conventional calibration which is different that of other low density ethylene-based polymers. The difference is captured in a relationship called the Y value. The Y value - LSCDF3 is determined by a GPC-LS characterization method, described below in the Test Method section. ("CDF" is the cumulative detection fraction). The low density ethylene-based polymer has a Y value of about 0.4 to about 10. [023] Methods for using a tubular reactor to form low density ethylene-based polymers are well known in the art. state of the art. The process is a
    [023] Methods for using a tubular reactor to form low density ethylene-based polymers are well known in the art. The process and a tubular polymerization reaction, where a partially fluid process, comprising ethylene is polymerized radically free, creating a highly exothermic reaction. The reaction occurs under operatively high pressure (1000 bar to 4000 bar), in a turbulent fluid flow process (therefore, low density ethylene polymer also referred to as "high pressure" polymers) at maximum temperatures in the reactor. 160 ° C to 360 ° C, while the initial reaction temperature is between 120 ° C to 200 ° C. At certain points along the tube, a portion of the heat produced during polymerization of the free radical can be removed through the tube wall. The typical conversion values for a single pass through a Vaira tubular reactor are about 20 to 40 percent. The tubular reactor system also includes at least one monomer recycling loop to improve conversion efficiency.
    [024] For the purpose of describing the process, a non-limiting tubular polymerization reaction system is shown in figure 1. The tube reactor system 100 has a tube 2 with a length typically from about 250 to about 2000 meters . The length and diameter of the tube affect the residence time and speed of the process fluid, as well as the addition of heat / removal capacity from the tube 2. Suitably, but not limiting, the reactor length can be between 100 and 3000 meters, and in some cases between 500 and 2000 meters. Tube 2 also has an internal working diameter of about 30 to about 100 mm based on the desired maximum result system, operating pressure variation, and the degree of flow turbulence for mixing and reaction. The internal working diameter can increase and decrease at one point along the tube 2 to accommodate different portions of the process, such as turbulence mixing, injection of the reaction and feed initiators, and process fluid regulator (ie, acceleration of the process). speed of the process fluid, at the cost of pressure loss).
    [025] With respect to figure 1 and the tube reactor system 100, a primary compressor 4, which can be a multistage compressor or two or more compressors running in parallel, is connected on its input side to a source of fresh monomer / monomer feed called fresh feed conduit 6 and a low pressure system recycling conduit 8. The low pressure system recycling conduit 8 is one of two handles for recycling the volatilized process fluid feed from of the refinement section of the tube reactor system 100 facing the front of the process. In the described processes, the recycling duct 8 of the low pressure system primarily contains ethylene, but it may contain unused comonomers and other process additives, such as residual chain transfer agents. Primary compressor 4 raises the pressure of the process fluid at a pressure of about 20 bar to about 275 bar.
    [026] Still with respect to figure 1, a second compressor, in some cases called hyper-compressor 5, which can be a multi-stage compressor, is connected at its entrance to the discharge of the primary compressor 4, as well as to second of two recycling stream called high pressure system recycling duct 26. The hyper-compressor 5 raises the pressure of the process fluid at an operating pressure of 1000 to 4000 bar.
    [027] The hyper-compressor 5 of the description can be an alternative piston compressor due to the high compression ratio between the primary compressor inlet and the reactor, as well as the high operating pressure of the process fluid reactor. The hyper-compressor can be a single-stage compressor for lower operating pressures in the reactor or a multi-stage compressor with a cooling inter-stage between some or all of the stages for higher operating pressures in the reactor.
    [028] The process fluid being discharged from the hyper-compressor 5 does not flow in a continuously stable manner, but instead "pulses" with each shock of the compressor. This is because the plunger within each stage opens and discharges the compressed process fluid in a step-like manner. The resulting flow discharge pulse can result in a pressure variation of + 10% or more in the operating pressure. A flow discharge cycle creating the system pressure that arises can have very long negative effects on the mechanical integrity of the process units, such as the hyper-compressor, the discharge line, and the reactor. Then, the reduction in the mechanical integrity of these subsystems can affect the total stability of the operation and the safety in terms of line of operation, although the stability of the process can be influenced by the pulsation of the flow and pressure. In addition, this is possible due to the geometry of the discharge line which, in individual discharge shocks from separate pistons, from the same compressor (such as from a multistage compressor with several discharge points), can overlap each other ( that is, to be partially or totally "in phase" with each other), resulting in an amplification in the resistance of the discharge pulsations during the combination in a stream of common process fluid. It is a good operational practice, therefore, to use static and active mechanical devices, such as pulsation holes and dampeners in the compressor discharge line to minimize not only the pressure that arises, but also to minimize the effect of the amplification. pressure pulse in the common discharge lines in the process and in the reactor system equipment.
    [029] After pressurization by the hyper-compressor 5, the process fluid is increased in the tube 2 through the conduit 12 as an upstream process feed stream. In some of the described processes, the process fluid is divided and fed to tube 2 at different feeding locations. In said processes, part of the process fluid is fed to tube 2 through conduit 12 as an upstream process feed stream to a first reaction zone and the other parts (depending on the number of divisions made in the process fluid) would be fed to tube 2 as a feed stream from the downstream process in other reaction zones through various conduits 14. The other reaction zones are located longitudinally along tube 2 below the first reaction zone. As previously stated, there may be more than one reaction zone.
    [030] In processes where there is more than one reaction zone, one or more free radical initiator ducts or catalysts 7 transport the initiator or catalyst to tube 2 near or at the beginning of each reaction zone. The injection of initiators or catalysts, depending on the desired ethylene-based polymer adduct, under the operating conditions of the process, initiates the reaction of the monomeric / comonomer materials. In the described processes, the main product of said reaction is a polymer based on ethylene and heat. The initiator or catalyst can be added to each reaction zone to improve the conversion of the monomer (and comonomer, if included) to process fluid as previously discussed. In a described process, different initiators or catalysts can be added to the process fluid in different reaction zones to ensure that the peak temperature is achieved close to the inspection point and to achieve multiple temperature target peaks.
    [031] Examples of free radical initiators used in the processes include oxygen-based initiators, such as organic peroxides (PO). Preferred initiators are t-butyl peroxy pivalate, di-t-butyl peroxide, t-butyl peroxy acetate, and t-butyl peroxy-2-ethylhexanoate, and mixtures thereof. These standard organic starters are used in conventional amounts between 0.0001 and 0.01 weight percent based on the weight of the high pressure feed.
    [032] Catalysts suitable for use to polymerize other polymers that can be mixed with the new LDPE described here, include any compound or combination of compounds that is adapted to prepare polymers of the desired composition or the like. Both catalysts, heterogeneous or homogeneous, and combinations thereof, can be used. In some embodiments, heterogeneous catalysts, including the well-known Ziegler-Natta compositions, especially Group 4 metal halides, supported on Group 2 metal halides or mixed halides and alkoxides and the well-known chrome or vanadium-based catalysts can be used. In some embodiments, the catalysts for use may be homogeneous catalysts comprising a relatively pure organometallic compound or metallic complex, especially a compound or complex based on metals selected from groups 3-10 or the Lanthanide series. If more than one catalyst is used in a system, it is preferred that any catalyst employed does not significantly and significantly affect the performance of the other catalyst under the conditions of polymerization. Desirably, no catalyst is reduced in activity by more than 25 percent, more preferably, more than 10 percent under polymerization conditions. Examples of preferred catalyst systems can be found in U.S. Patent Nos .: US 5,272,236 (Lai, et al.); US 5,278,272 (Lai, et al.); US 6,054,544 (Finlayson, et al.); US 6,335,410 (Finlayson, et al.); US 6,723,810 (Finlayson, et al.); in international publications Nos .: WO 2003/091262 (Boussie, et al.); WO 2007/136497 (Konze, et al.); WO 2007/136506 (Konze, et al.); WO 2007/136495 (Konze, et al.); and 2007/136496 (Aboelella, et al.). Other suitable catalysts can be found in the publication of US patent application No .: US 2007/0167578 (Arriola, et al.).
    [033] The resulting free radical polymerization reaction in the ethylene-based polymer adduct described occurs in each reaction zone, where the initiator or catalyst is present. The reaction is an exothermic reaction that produces a large amount of heat. Without cooling, the adiabatic temperature rises in the process fluid and the ethylene-based polymer adduct (which absorbs and retains heat) would result in an unfavorable reaction. Said reaction may include the decomposition of ethylene (where ethylene and polyethylene break down in a reaction accompanied by a rapid rise in temperature in the base product).
    [034] In some processes, the temperature of the process fluid is reduced by removing heat through the wall of tube 2 by inducing a heat flow with a heat removal medium. A heat removal means is a fluid used to absorb and remove heat from the reactor system in tube 100, such as, an ethylene glycol, water, or air. When the heat removal medium is a liquid, a heat exchanger 30, which can be as simple as a 1-1 cooling jacket, or a complex multi-pass cooling system, can be used to affect heat transfer and cool the process fluid and ethylene-based polymer adduct. Non-limiting examples of heat exchangers and techniques for removing heat are described in Perry, Robert H., ed., Perry's Chemical Engineer’s Handbook, Chp. 10, McGraw-Hill Book Co. (6th ed., 1984) and McCabe, Warren L, et al., Unit Operations of Chemical Engineering, McGraw-Hill, Inc. (5th ed., 1993). When the heat removal medium is a gas, fans can be used to converge the heat out of the reactor tube 2. The heat removal medium will have a mass flow rate, inlet temperature, and temperature of exit. When the heat removal medium is used to remove heat from the tube reactor system 100, the inlet temperature of the heat removal medium into the heat exchanger 30 will be less than the outlet temperature. The difference between the inlet temperature and the outlet temperature at a given mass flow rate is reflected in the heat removed from the process, resulting in the heat capacity of the heat removal medium and the ability of tube 2 to transfer heat to the medium. heat removal.
    [035] In some processes, heat transfer agents (CTAs) are added in order to mix as homogeneously as possible with the process fluid before introduction to tube 2. Depending on the physical structure of the tube reactor system 100 and of the chemical characteristics of the process fluid and the CTAs, the said mixture can be achieved through the injection of CTAs at the entrance of the reinforced compressor ("booster") 21 for the recycling duct of the low pressure system 8, at the entrance of the primary compressor 4, at the entrance of the hyper-compressor 5, at the exit of the hyper-compressor 5, at the entrance of the tube 2, or together with the first injection of peroxide. For the process shown in figure 1, the CTAs are injected into the reactor system 100 via the CTA 23 source, at the entrance of the primary compressor 4.
    [036] Although not shown in the tube reactor system 100 for more details in figure 1, selective feeding of the CTAs to the tube reactor 2 is possible. In some processes, the process fluid is divided into an upstream process feed stream and at least one downstream process feed stream after pressurization via hyper-compressor 5. In such cases, CTAs can be fed into of tube 2 selectively because they are injected into conduits 12 or 14 instead of using the CTA 23 source, as shown in figure 1. In specific cases, CTAs can be injected from the CTA 23 source only into the current upstream process feed via duct 12. In processes where the hyper-compressor 5 contains multiple stages or series, the process fluid can be divided into an upstream process feed and at least one downstream process feed stream at the inlet of the hyper-compressor 5. In the referred cases, the CTAs can be selectively fed from a source of CTA 23 both within the process feed upstream and at least in u a downstream process feed prior to pressurization by hyper-compressor 5, or as previously stated, inside conduit 12 or conduit 14 after pressurization. This flexibility in the process described in relation to the injection of CTAs from the source of CTA 23 allows the selective injection of CTAs only within the first reaction zone or only within some or all of at least one of the other reaction zones. It also allows the injection of different CTAs, including CTAs with different constant chain transfer characteristics (Cs), to be injected from the source of CTA 23 into different zones to improve the performance of the reaction system and the properties of the adduct of ethylene-based polymer.
    [037] In some processes, the source of CTA 23 can be comprised of several sources of individual chain transfer agents. Although not shown in Figure 1, the sources of individual chain transfer agents can be distributed individually or combined within a common stream that is injected into a common spot.
    [038] Referring again to figure 1, and to the reactor system in tubes 100, a mixture of polymer based on ethylene, formed from the reaction of unreacted monomer (and comonomer) and unused feed, such as solvents and CTAs, or degradation products and side reaction products pass from the outlet of the tube 16 to the part of the process separation. The process separation and recycling part of the tube reactor system 100 includes a high pressure separator (HPS) 18, which receives the polymer product and process fluid mixture from the outlet of the tube 2. The HPS 18 separates much of the monomers from the ethylene-based polymer adduct. The HPS 18 tails carry the polymer adduct and any remaining unreacted monomer / comonomer and other unused feeds that can be dissolved with the polymer adduct to the low pressure separator (LPS) 20. A clear upper pressure current passes through the recycling duct 26 of the high pressure system, which may include a refining system 24 to cool and purify the inert current and decontamination gases, and rewire the process fluid from the primary compressor 4 for hyper-compressor 5.
    [039] With respect to figure 1, LPS 20 separates any remaining monomer / comonomer and unused feed from the polymer adduct by operating at slightly higher atmospheric pressure or under vacuum conditions. The LPS 20 operates in a pressure range of about 4 to about 1.2 bar absolute to extract incoming gases. The adduct of the resulting ethylene-based polymer, still fused in processing, passes through the remainder of LPS 20, to the finalization steps, such as extrusion, tempering, and pelletizing. The light from the LPS 20 passes through the recycling duct 8 of the low pressure system where its pressure is increased around atmospheric pressure to at least the pressure required for the proper operation of the primary compressor 4. The low pressure amplifying compressor 21 can have a number of stages. The resulting product polymer is degassed with volatile reagents and the entire efficiency of the system is improved by recycling unused monomers in front of the 100 reactor system.
    [040] The recycling streams in both the low pressure system's recycling line 8 and the high pressure system's recycling line 26 typically contain a portion of the chain transfer agents. Most often, the recycling duct 26 of the high pressure system will more often contain a significant concentration of low-Cs transfer agent when it is not completely consumed during the reaction process. In some of the described processes, during the reach of the declared stable production, the quantity of fresh low-CS CTA for the process, via source of CTA 23 is relatively smaller when compared to the quantity present in the high and low recycling lines 26 and 8 pressure, respectively.
    [041] End-use products made using the ethylene-based polymers described include all types of films (for example, blowing, casting and extrusion coatings (monolayers or multi-layers), molded articles (for example, molding by blowing and roto-molded articles), coating and formulations for wires and cables, application of crosslinkers, foams (for example, blowing / insufflation with open or closed cells), and other thermoplastic applications The ethylene-based polymers described are also useful as a mixing component with other polyolefins, such as, polymers described in provisional U.S. Patent Application No .: US 61 / 165,065, DOWLEX - linear low density polyethylene (LLDPE), ENGAGE - polyolefin elastomers, AFFINITY - plastomers polyolefins, INFUSE - olefin block copolymers, VERSIFY - plastomers and elastomers - all made by "The Dow Chemical Company", and EXACT - polymers, EXCEED polymers, VISTAMAXX - all made by ExxonMobil. ASTUTE and SCLAIR made by "Nova Chemicals" can also be mixed with the new LDPE described here.
    [042] The types of films that can be produced as end-use products from the described ethylene-based polymers include laminating films, silage films, sealants, silage packaging, expansion films, bi-axially polyethylene oriented, display packaging, shrink films, overwraps, masking films, heavy duty shipping bags and regular release. In addition, blowing, casting and extrusion coatings (monolayers or multi-layers) can also be produced using the ethylene-based polymers described. Definitions:
    [043] The terms "mixture" or "mixture of polymers" generally mean a mixture of two or more polymers. A mixture may or may not be miscible (phase not separated at the molecular level). A mixture may or may not have a separate phase A mixture may or may not contain one or more domain configurations, as determined from electron transmission spectroscopy, light scattering, X-ray scattering, and other methods known in the art.
    [044] The term "comparable" means similar or gender.
    [045] The term "composition" includes a mixture of materials comprising the composition, as well as reaction products and decomposition products formed from the interaction and reaction between the materials in the composition.
    [046] The term "ethylene-based polymer" refers to a polymer that contains more than 50 mol percent of polymerized ethylene monomer (based on the total amount of polymerizable monomers) and, optionally, can contain at least a comonomer. An ethylene homopolymer is an ethylene-based polymer.
    [047] The term "ethylene / a-olefin interpolymer" refers to an interpolymer that contains more than 50 mol percent of the polymerizable ethylene monomer (based on the total amount of polymerizable monomers), and, optionally, can contain at least one comonomer. An ethylene homopolymer is an ethylene-based polymer.
    [048] The term "ethylene / alpha-olefin interpolymer" refers to an interpolymer that contains more than 50 mol percent of polymerized ethylene monomer (based on the total amount of polymerizable monomers), and at least one α-olefin .
    [049] The term "homopolymer" is a polymer that contains only a single type of monomer.
    [050] The term "interpolymer" refers to polymers prepared by the polymerization of at least two different types of monomers. The term interpolymer includes copolymers, usually used to refer to polymers prepared from two different monomers, and polymers prepared from more than two different types of monomers, such as terpolymers.
    [051] The term "LDPE" can also be referred to as a "high pressure ethylene polymer" or "highly branched polyethylene" and is defined as meaning a polymer that is partially or completely homopolymerized in autoclave or tubular reactors at pressures above 13, 000 psig with the use of free radical initiators, such as peroxides (see, for example, U.S. Patent No .: US 4,599,392 (McKinney, et al.)).
    [052] The term "polymer" refers to a compound prepared by polymerization monomers, whether of the same or a different type of monomer. The term polymer encompasses the terms "homopolymers" and "interpolymers".
    [053] The term "standard deviation" is the quantity that measures the spread or spread of the distribution from an average value. See, Perry, Robert H., Ed., Perry's Chemical Engineer's handbook, McGraw-Hill Book Co. (6th ed., 1984), also Miller, Irwin, Probability and Statistics for Engineers, Prentice Hall (4th ed., 1990) .
    [054] The terms "steady state" and "steady state condition (s)" represent a condition where the properties of any part of a system are constant during a process. See, Lewis, Richard J., Mr. Hawley's Condensed Chemical Dictionary, Wiley-Interscience (15th Ed., 2007); also Himmelblau, David M., Basic Principles and Calculations in Chemical Engineering, Prentice Hall (5th ed., 1989).
    [055] The term "GPC-LS characterization Y value" is also defined as the term "LSCDF3" and mathematically calculated in equations 14-16 below. Test methods:
    [056] Density
    [057] Samples for density measurement are prepared according to ASTM D 1928. Measurements are made within one hour of pressing the sample using ASTM D 792, Method B.
    [058] Fusion index: c
    [059] The melting index, or I2, is measured according to ASTM D 1238, Condition 190 ° C / 2.16 kg. 10 is measured with ASTM D 1238, Condition 190 ° C / 106 kg.
    [060] Resistance to melting:
    [061] Melt strength is measured at 190 ° C using a Gõettfert Rheotenns 71.97 (Gõettfert Inc .; Rock Hill, SC), feeding the melt with a Gõettfert Rheotester 2000 capillary rheometer, equipped with a flat entry angle (180 degrees) in length of 30 mm and diameter of 2 mm. The pellets were fed into the barrel (L = 300 mm, Diameter = 12 mm), compressed and left to melt for 10 minutes, before being extruded, at a constant piston speed of 0.265 mm / s corresponding to the shear rate on the wall of 38.2 s-1 in the given diameter of the mold. The extrudate passed through the wheels of the Rheotenns located 100 mm below the mold outlet and was pulled down through the wheels at an acceleration rate of 2.4 mm / s2. The force (in cN) exerted on the wheels was recorded as a function of the speed of the wheels (in mm / s). Fusion strength was reported as the plateau force (cN) before the breaking trend. Zero shear viscosity:
    [062] Slip measurement specimens were prepared on an upper bench of the Tetrahedron programmable press. The program maintained the melting at 177 ° C for 5 minutes at a pressure of 107 Pa. The cracks were then removed at the top of the bench by cooling to room temperature. The round test specimens were then cut into the mold from plates using a perforated press and a portable mold with a diameter of 25 mm. The specimens are about 1.8 mm thick.
    [063] The zero shear viscosities were obtained via slip tests that were conducted in a rheometer with controlled conditions AR-G2 (TA Instruments; New Castle, Del) using parallel plates of 25 mm in diameter at 190 ° C. Two thousand ppm of antioxidant, a mixture of 2: 1 and IRGAFOS 168 and IRGANOX 1010 (Ciba Specially Chemicals; Glattbrugg, Switzerland) was added to stabilize each sample before compression molding. At the test temperature, a compression molded sample disk was inserted between the plates and left to start equilibration for 5 minutes. The upper plate was then reduced to 50 mm above the desired test interval (1.5 mm). Any superfluous material was removed and the upper plate was reduced to the desired interval. Measurements were made under nitrogen sparging at a flow rate of 5 L / min. The non-slip time was represented by 5 hours.
    [064] A low shear condition of 20 Pa was applied to all samples to ensure that the shear rate in stable condition is low enough to be in the Newtonian region. The resulting shear rates under stable conditions are in the range of 10 “3 to 10-4 s 1 for all samples in this study. The stable condition was determined by taking a linear regression for all data in the last 10% of the interval window, at log points (J (t)) vs. log (t), where J (t) conforms and t is the slip time. If the slope of the linear regression is greater than 0.97, the stable condition is considered to be achieved, then the slip test is stopped. In all cases in this study, the samples reached a stable condition within 5 hours. The shear rate in the stable condition is determined from the slope of the linear regression of all data points in the window for the last 10% of the time, at points £ versus t, where £ is the stress. The zero shear viscosity is determined from the proportion of the applied stress condition (20 Pa) to a shear rate in the stable condition.
    [065] The small amplitude oscillatory shear test is conducted before and after the slip test of the same specimen from 0.1 to 100 rad / s at 10% tension. The values of the complex viscosity of two tests were compared. If the difference in viscosity values at 0.1 rad / s is greater than 5%, the sample is considered to have been degraded during the slip test, and the result is discarded. DSC:
    [066] Differential scanning calorimetry (DSC) can be used to measure the melting and crystallization behavior of a polymer over a wide temperature range. For example, the TA Q1000 DSC instrument, equipped with an RCS (refrigerated cooling system) and an auto-sampler was used to perform this analysis. During the test, a 50 ml / minute nitrogen purification gas flow was used. Each sample was melted by pressure on a thin film at about 175 ° C; the molten sample was then cooled in air, at room temperature (~ 25 ° C). A specimen of 3 ~ 10 mg, with 6 mm in diameter was extracted from the chilled, weighed polymer, placed in a light aluminum pan (ca 50 mg), and closed by crimping ("crimped shut"). The analysis was then performed to determine its thermal property.
    [067] The thermal behavior of the sample was determined by displacing the sample between high and low temperatures, to create a heat flow versus a temperature profile. First, the sample is quickly heated to 180 ° C and kept isothermal for 3 minutes in order to remove its thermal history. Then, the sample was cooled to ~ 40 ° C at a cooling rate of 10 ° C / minute and kept isothermal at -40 ° C for 3 minutes. The sample was then heated to 150 ° C (this is the "second heat displacement") at a heating rate of 10 ° C / minute. The cooling and second heating curves were recorded. The cooling curve was analyzed through the extreme points of the baseline, represented by the start of crystallization at -20 ° C. The heating curve was analyzed through the extreme points of the baseline, represented at -20 ° C for the end of the fusion. The values determined were the melting temperature peaks (Tm), crystallization temperature peak (Tc), melting heat (Hf) (in Joules per gram), and the% crystallinity calculated for the polyethylene sample using the Equation 1:
    [068] The heat of fusion (Hf) and the peak melting temperature are reported from the second heating curve. The peak crystallization temperature is determined from the cooling curve.
    [069] Fourier infrared transformation spectroscopy (FTIR):
    [070] FTIR unsaturation was measured on a Thermo Nicolet model Nexus 470 device. The following procedures were determined: - Metals per 1000 C: - Trans per 1000C; ASTM D2238 ASTM D6248 - Vinyls per 1000C: ASTM D6249 - Vinyls per 1000C: ASTM D3124 - carbonyl for thickness ratio. The proportion of the carbonyl area to thickness was determined as:
    Film test conditions:
    [071] The following physical properties were measured on the films produced: - surface and internal opacity, total (complete): The samples measured for internal opacity and complete opacity were sampled and prepared according to ASTM D 1003. The internal opacity was obtained via compatible refractive index, using mineral oil on both sides of the films. A Hazegard Plus device (BYK-Gardner, USA; Columbia, MD) was used for the test. Surface opacity was determined as the difference between total opacity and internal opacity as shown in Equation 3. Surface opacity tends to be reported as the surface roughness in the film, where the surface opacity increases with increasing roughness the surface. The surface opacity for the internal opacity ratio is the surface opacity value divided by the internal opacity value, as shown in Equation 4.
    S / I = Surface opacity / internal opacity (Eq. 4) - 45 ° brightness and 60 ° brightness: ASTM D-2457. - 1% secant module and 2% secant module in the MD (machine direction) and Cd (transversal direction): ASTM D-882. - Resistance to breakage MD and CD Elmendorf: ASTM D-1922. - MD and CD voltage resistance: ASTM D-882 - dart impact strength (ASTM D-1709). - Puncture resistance: drilling is measured on an Instron Model 4201 with a version of the Sintech Testworks 3.10 software. The size of the specimen is 6 "x 6" and 4 measurements were taken to determine an average drilling value. The film was conditioned for 40 hours after film production and at least 24 hours in a laboratory controlled ASTM. A 100 pound cell load was used with a round type funnel / retainer. The type is a 4-inch circular specimen. The drill rig has a one inch diameter of a polished stainless steel ball (on a 0.25 inch rod), with a maximum travel length of 7.5 inches. There is no measure of length; the probe is as close as possible, but does not touch the specimen. The crosshead speed is 10 "/ minutes. The thickness is measured in half of the specimen. The thickness of the film, the travel distance of the crosshead, and peak load are used to determine the perforation of the software. drilling rig is cleaned using a "Kim-wipe" after each specimen - 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). -% free shrinkage: a single layer square film with a dimension of 10 , 16 cm x 10.16 cm is cut by a cutting press, in a sample of the film along the edges of the machine direction (MD) and in the transverse direction (CD). The film is then placed in a film retainer and the film retainer is immersed in a hot oil bath at 150 ° C for 30 seconds. The retainer is then removed from the oil bath. After the oil is drained , the length of the film is measured at multiple locations in each direction and the average is taken at the final length. The% of free retraction is determined from Equation 5.

    [072] Gel permeation chromatography with triple detector (TDGPC):
    [073] The triple detector gel permeation chromatography system (3D-GPC or TDGPC) consists of a Waters 150C high temperature chromatograph (Milford, Mass) (other suitable high temperature GPC instruments include Polymer Laboratories (Shropshire, UK ) Model 210 and Model 220), equipped with a built-in differential refractometer (IR). Additional detectors may include an IR4 infrared detector, obtained from Polymer ChAR (Valencia, Spain), Precision Detectors (Amherst, Mss.) 2-angle laser light scattering detector (LS) Model 2040, and a Viscotek (Houston , Tex.), Viscometer of the 150R 4-capillary solution. A GPC with the latter two independent detectors and at least one of the previous detectors is sometimes referred to as "3D-GPC" or "TDGPC" although the term "GPC" alone refers to the conventional GPC. Depending on the sample, either the 15 ° angle or the 90 ° angle of the light scattering detector can be used for the purpose of calculation. Data collection is performed using Viscotek Tri-SEC software, version 3, and a Viscotek DM400 4- channel data manager. The system is also equipped with an in-line solvent degassing device obtained from Polymer Laboratories (Shropshire, England).
    [074] Appropriate high temperature GPC columns can be used, such as four 30 cm long Shodex HT803, 13 micron columns, or four 30 cm columns, 20 micron Polymer Labs, in mixed size packages. of pores (MixA LS, Polymer Labs). The sample carousel compartment is operated at 140 ° C and the column compartment is operated at 150 ° C. The samples are prepared in a concentration of 0.1 gram of polymer in 50 milliliters of solvent. The chromatographic solvent and the sample preparation solvent contain 200 ppm of trichlorobenzene (TCB). Both solvents are spread with nitrogen. The polyethylene samples are gently stirred at 160 ° C for four hours. The injection volume is 200 microliters. The flow rate through the GPC is fixed at 1 ml / minute.
    [075] The fixed GPC column is calibrated through 21 runs with limited molecular weight distribution of the polystyrene standards. The molecular weight (MW) of the standard ranges from 580 to 8,400,000, and the standards were contained in 6 cocktail mixtures. Each standard mixture has at least one of ten separations between the individual molecular weights. Standard mixtures were purchased from Polymer Laboratories. Polystyrene standards are prepared at 0.025 g in 50 ml of solvents for molecular weights equal to or greater than 1,000,000 and 0.05 g in 50 ml of solvent for molecular weights less than 1,000,000. The polystyrene standards were dissolved at 80 ° C with gentle stirring for 30 minutes. Mixtures of limited standards were first run in order to decrease the higher molecular weight component to minimize degradation. The molecular weight peaks of standard polystyrene are converted to polystyrene molecular weight using Equation 6 (as described in Williams and Ward, "J. Polym. Sci.", Polym. Letters, 6, 621 (1968):
    where M is the molecular weight of polyethylene or polystyrene (as marked), and B is equal to 1.0. It is known to those skilled in the art that A can be in a range of about 0.38 to about 0.44 and is determined in the calibration period using a wide polyethylene standard, as highlighted in the gpcBR branching index by the 3D- GPC, infra, and specifically equations 11-13. The use of this polyethylene calibration method to obtain molecular weight values, such as molecular weight distribution (MWD or Mw / Mn), and reported statistics, is defined here as the modified Williams and Ward method.
    [076] The systematic approach to the determination of multiple compensated detectors is performed in a manner consistent with those published by Balke, Mourey, et al., (Mourey and Balke, Chromatography Polym., Chapter 12, (1992)) (Balke, Thitiratsukul, Lew, Cheung, Mourey, Chromatography Polym., Chapter 13, (1992)), optimizing the triple detector log (average weight of molecular weight Mw, and intrinsic viscosity) results from the wide polystyrene of Dow 1683 (American Polymer Standards Corp .; Mentor, OH) or its equivalent for limited standard column calibration results in the standard limited polystyrene calibration curve. Molecular weight data are obtained in a manner consistent 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)). The total injected concentration used to determine the molecular weight was obtained from the mass detector area and the mass detector constant derived from an appropriate linear polyethylene homopolymer, or one of the average weighted polyethylene standards of the known molecular weight. The calculated molecular weights are obtained using a constant light spread, derived from one or more of the mentioned polyethylene standards and a concentration coefficient of the refractive index, dn / dc, 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 in excess of about 50,000 Daltons. and be followed up using the methods described by the manufacturer or alternatively using published values of linear standards, such as Standard Reference Materials (SEM) 1475a, 1482a, 1483, or 1484a. Chromatographic concentrations are assumed to be low enough to eliminate the effects of the second targeting of the viral coefficient (effects of concentration on molecular weight). gpcBR branching index by 3D-GPC
    [077] In 3D-GPC configurations, polyethylene and polystyrene standards can be used to mediate the constant Mark-Houwink, K and a, independently for each of the two types of polymers, polystyrene and polyethylene. These can be used to refine the equivalent molecular weights of the polyethylenes, Williams and Ward, in the application of the following methods.
    [078] The gpcBR branching index is determined first by calibrating the light scattering, viscosity, and concentration detectors, as previously described, The baselines are then subtracted from the light scattering, viscometer, and concentration chromatograms. The integration windows are then fixed to guarantee the integration of all low molecular weight retention volume ranges in the light scattering and chromatograms of viscometers that indicate the presence of the detectable polymer of the refractive index chromatograms. Linear polyethylene standards are then used to establish Mark-Houwink constants for polyethylene and polystyrene as previously described. When obtaining the constants, the two values are used to construct two conventional linear calibration references for the molecular weight of the polyethylene and the intrinsic viscosity of the polyethylene, as a function of the elution volume, as shown in equations 7

    [079] The gpcBR branching index is a robust method for characterizing the long chain branching as described in Yau, Wallace W., "Examples of Using 3D-GPC - TREF for Polyolefin Characterization", Macromol., Symp., 2007 , 257, 29-45. The index avoids the calculation of the 3D-GPC portion-by-portion, traditionally used in the determination of g 'values and the calculation of the branching frequency in favor of all areas of polymer detection. From the 3D-GPC data, one can obtain the absolute sample volume of the average molecular weight (MWfAbs) by the light scattering detector (LS) using the peak area method. The method avoids the proportion of the portion by portion of the light scattering detector signal over the concentration detection signal as required in a traditional g 'determination.
    [080] With 3D-GPC, the absolute average weight of the molecular weight ("Mw, Abs") and the intrinsic viscosity are also obtained independently using equations 9 and 10:

    [081] The calculation of the area in equation 9 offers more precision because as an area of the complete sample it is much less sensitive to variation caused by the noise of the detector and the 3D-GPC configurations in the baseline and integration limits. Most importantly, the peak area calculations are not affected by the detector volume compensation. Similarly, the intrinsic viscosity of the high-precision (IV) sample is obtained by the area method shown in Equation 10:

    [082] Where DP, keeps the differential pressure signal monitored directly from the inline viscometer.
    [083] To determine the gpcBR branching index, the elution area of the light scattering for the sample polymer is used to determine the molecular weight of the sample. The elution area of the viscosity detector for the sample polymer is used to determine the intrinsic viscosity (IV o [η]) of the sample.
    [084] Initially, the molecular weight and intrinsic viscosity for a standard linear polyethylene sample, such as SRM1475a or an equivalent, are determined using conventional calibration ("cc") for both the molecular weight and the intrinsic viscosity as the function of the elution volume, by equations 11 and 12:

    [085] Equation 13 is used to determine the gpcBR branch index:

    [086] Where [η] is the measured intrinsic viscosity, [η] Cc is the intrinsic viscosity obtained from conventional calibration, Mw is the average weight of the measured molecular weight, and Mw, cc is the average molecular weight of the conventional calibration. . The average weight of the molecular weight by the spread of light (LS) using Equation (9) is commonly referred to as an "absolute average weight of the molecular weight" or "MWfAbs". The Mw, cc of equation (11) using the conventional GPC molecular weight calibration curve ("conventional calibration") is often referred to as a "main molecular weight of the polymer chain", "average conventional molecular weight", and MW, GPC •
    [087] All statistical values with the subscripts "cc" are determined using their respective elution volumes, the corresponding conventional calibration as previously described, and the concentration (C ±) derived from the retention volume of the molecular weight calibration. Unsubscribed values are the values measured based on the mass detector, LALLS, and viscometer areas. The KPE value is adjusted interactively until the linear reference sample has a measured gpcBR value of zero. For example, the final values for a and log K for gpcBR determination in this particular case are 0.725 and -3.355, respectively, for polyethylene, and 0.722 and -3.993 for polystyrene, respectively.
    [088] Once the K and a values have been determined using the procedures discussed previously, the procedure is repeated using the branched samples. Branched samples are analyzed using the final Mark-Houwink constants as the best "cc" values and equations 9 to 12 are applied.
    [089] The interpretation that gpcBR is linear in sequence. For linear polymers, the gpcBR calculated from Equation 13 will be close to zero since the values measured by LS and viscometry 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, because the measured molecular weight of the polymer will be greater than the calculated Mw, cc, and the calculated IVCC will be greater than the IV of the measured polymer. In fact, the gpcBR value represents the fractional IV change due to the effective molecular size contraction as a result of the polymer branch. A gpcBR value of 0.5 or 2.0 would mean an effective IV molecular size contraction at the 50 level. % and 200%, respectively, versus a linear polymer molecule of equivalent weight.
    [090] For these particular examples, the advantage of using gpcBR over a conventional "g-index" and branching frequency calculations is due to the high 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 3D-BPC detector at high molecular weights from the concentration detector. Errors in the alignment of the detector volume also do not affect the accuracy of the gpcBR index determination. Characterization GPC-LS:
    [091] Analysis of a response curve of the normalized concentration-LS chromatogram for a particular sample using a predetermined molecular weight range that is useful in the differential embodiment of comparatively low density commercially available ethylene analogs and polymers .
    [092] The "GPC-LS characterization" parameter, value Y, is designed to capture the unique combination of MWD and the GPC-LS profile for a specific material. Figures 2 to 4 provide the examples and the guide for using the GPC-LS characterization method to identify embodiments of the invention.
    [093] An ethylene-based polymer that has long chain branches, such as low-density ethylene-based polymers, can be differentiated by using an analysis technique called "GPC-LS characterization". In the GPC-LS characterization method, the determination is made using the light scattering detector (LS) response for a sample processed by a conventionally calibrated 3D-GPC ("cc-GPC") over a sample molecular weight range . The molecular weights of the sample are converted to logarithmic values for the purpose of scale. The LS response is "a normalized concentration" so called the LS response can be compared between samples, as are known in the art, non-normalized LS signals can vary widely from sample to sample without normalization. When organized, the logarithmic values of the cc-GPC molecular weight range and the normalized concentration values LS form a curve of the normalized concentration chromatogram LS, as shown in figures 2 to 4.
    [094] Since the curve of the normalized concentration chromatogram LS is available, the determination of the GPC-LS characterization value is obvious. In the GPC-LS characterization method, a GPC-LS characterization value (Y) is determined using the following equations:

    [095] Where Abs () is the absolute mathematical value function.
    [096] Essentially, the GPC-LS characterization value is a relationship between two associated areas (A and B) and a one-line slope index (x) between two points on the curve of the LS normalized concentration chromatogram in the logarithmic values of two cc-GPC molecular weight values specified. The cc-GPC molecular weight values meet the fraction of the molecular weight in parentheses that is known to contain the polymer chains with long chain branching.
    [097] The first step in the analysis is the production of the LS normalized concentration chromatogram curve representing the LS normalized concentration response values versus the logarithmic values of the cc-GPC molecular weights for the polymer being examined.
    [098] The second step is to draw a straight line between two points on the curve of the normalized concentration chromatogram - LS. The straight line and the points will provide the basis for determining area A and B. The two points, a first point and a second point, are located on the curve of the normalized concentration chromatogram-LS and represent the concentration response values normalized LS (a first and a second normalized concentration response value-LS) in the logarithmic values for the two cc-GPC molecular weight values (a first and a second logarithmic cc-GPC molecular weight value). The first point (for example, intersection 1 in figure 2) is defined as the normalized concentration chromatogram curve-LS (representing the first normalized concentration response value-LS), corresponding to the logarithmic value of the cc-GPC molecular weight 200,000 grams / mol (representing the first logarithmic cc-GPC molecular weight value), which is a value of approximately 5.3010. The second point (intersection 2 in figure 2) is defined as the curve of the normalized concentration chromatogram LS in the normalized concentration response value LS (representing the second LS normalized concentration response value LS) corresponding to a logarithmic weight value molecular cc-GPC of 1,150,000 grams / mol (representing the logarithmic cc-GPC molecular weight value), which is a value of approximately 6.0607. It is known from the state of the art that differentiation in long chain branching is typically shown around IM (1 x 106) gram / mol, cc-GPC molecular weight.
    [099] The third step is to determine the area A, between the straight line and the curve of the normalized concentration chromatogram LS between two logarithmic cc-GPC molecular weight values. Area A is defined as the value of Al plus A2. In preferred embodiments, area a is defined for the range between the logarithmic value of the molecular weight of cc-GPC 200,000 gram / mol and the logarithmic value of the cc-GPC molecular weight 1,150,000 gram / mol.
    [100] Al is defined as the boundary area between the straight line and the curve of the LS normalized chromatogram where the normalized concentration-LS response value of the straight line is greater than the normalized concentration-LS response value for the curve normalized concentration chromatogram-LS between the two logarithmic cc-GPC molecular weight values.
    [101] As can be seen in figure 2, the area defined as Al fills the entire range between the two logarithmic cc-GPC molecular weights, therefore, A = Al. In many cases, the straight line will be "above" the curve of the normalized concentration chromatogram LS for the logarithmic cc-GPC molecular weight range and will not intersect with the curve of the normalized concentration chromatogram-LS except at intersection 1 and 2. In these cases, A = Al = a positive value, and A2 = 0.
    [102] A2 is defined as the inverse of Al. A2 is the connected area between the straight line and the curve of the normalized concentration-LS chromatogram where the response of the normalized concentration-LS of the straight line is less than the response of the normalized concentration -LS for the normalized concentration chromatogram-LS curve between the two logarithmic cc-GPC molecular weight values. For the example shown in figure 3, A2 is the area between the normalized concentration response curve-LS and the straight line between intersection 1 and 2. In these cases, A = A2 = a negative value, and Al = 0.
    [103] In some embodiments, as can be seen in figure 4, the straight line can intersect with the curve of the normalized concentration chromatogram LS at at least one other point between intersection 1 and 2 (see figure 4 in "Points of additional intersections "). In said situation, Al is determined as previously defined. For the example shown in figure 4, Al would be a positive area between the curve of the normalized concentration chromatogram LS and the straight line between the logarithmic cc-GPC molecular weight value of approximately 5.8 and the cc- GPC 200,000 gram / mol. In these situations, A2 is determined as previously defined. For the example shown in figure 4, A2 is the negative area between the normalized concentration response cure LS and the straight line between the logarithmic cc-GPC molecular weight value of approximately 5.8 and the cc molecular weight logarithmic value. -GPC of 1,150,000 gram / mol.
    [104] When calculating a total value for A, A is again defined as area Al (positive value), plus area A2 (negative value). In some embodiments, as can be graphically in figure 4, the total value for A can again be both positive and negative.
    [105] The fourth step is to determine the area B under the curve of the LS normalized concentration chromatogram for the logarithmic cc-GPC molecular weight range. B is defined as the area under the curve of the normalized concentration chromatogram LS between the two logarithmic cc-GPC molecular weight values. Area B does not depend on the analysis of area A.
    [106] The fifth step is to determine the value of x, the value of the slope index. The x value is an indexing factor that counts for the slope of the straight line established to determine areas A and B. The x value is not the slope of the straight line, however, it represents a reflective value of the difference between the points 1 and 2. The value of x is defined by Equation 17:
    where the term "LSresponse" is the normalized concentration response values LS for intersection 1 and 2, respectively, and the terms "log MW" are the logarithmic cc-GPC molecular weights for intersection 1 and 2, respectively. In some embodiments, the straight line can intersect the curve of the normalized chromatogram LS at least once between intercepts 1 and 2.
    [107] Finally, once x, A, and B are established, the GPC-LS characterization value (Y) is determined by using Equations 14-15 previously presented, repeated below: Y = LSCDF3 (Equation 14)
    Where, Abs () is the absolute mathematical value function.
    [108] Process information related to Examples 1 to 6 (ex. 1-6) and Comparative Example 9 (CE9):
    [109] In the discussion of Examples and Comparative Examples, several terms are defined. There are six exemplary compositions and sets of process information for its creation: Example 1 - Example 6. There is a composition for a comparative example and a set of process information. The same process series was used to create comparative Example 9 and Examples 1 to 6.
    [110] When process conditions are discussed and compared, process conditions can be referred to by your product designation (for example, process conditions for producing the product of Example 1) can be referred to as "process of Example 1" .
    [111] Example 1 - Example 6, as well as Comparative Example 9, are produced in the same process reaction system, therefore, in reference to the same equipment between runs, the physical process and its units are analogous to each other. Figure 5 illustrates a simple block diagram of the process reaction system used to produce the aforementioned Examples and Comparative Examples.
    [112] The process reaction system in Figure 5 is a partially closed high pressure loop (looping) recycling system, the low density polyethylene production system. The process reaction system is comprised of a feed line 1 of fresh ethylene; an "BP" amplifier / primary compressor, a "hyper" hyper-compressor, a three-zone tube reactor is made up of 155 high-pressure tubes that are 9.14 meters long. The tube reactor consists of a first reaction feed zone; a first peroxide initiator conduit 3 connected to a first source of peroxide initiator # 11; a second peroxide initiator conduit 4 connected to the second source of peroxide initiator 12; a third peroxide initiator conduit 5 connected to a second source of peroxide initiator 12; cooling housings (using high pressure water) are mounted around the outer housing of the tube reactor and the preheater; a high pressure separator "HPS"; a high pressure recycling line 7; a low pressure separator " LPS "; a low pressure recycling line 9; and a chain transfer agent 13 (CTA) supply system.
    [113] The tube reactor also comprises three reaction zones demarcated by the locations of the peroxide injection points. The tube reactor is 1316 meters long. The feed of the first reaction zone is connected to the front of the 0 meter tube reactor and feeds a portion of the process fluid within the first reaction zone. The first reaction zone starts at injection point # 1 (box 3, in figure 5), which is located 120 meters below the front tube of the tube reactor and ends at injection point # 2 (box 4 in figure 5 ). The first peroxide initiator is connected to the tube reactor at injection point # 1 (box 3 in figure 5). The second reaction zone starts at the injection point # 2 (box 4 in figure 5), which is 520 meters down the tube, in front of the tube reactor. The second reaction zone ends at injection point # 3 (box 5 in figure 5). The third reaction zone starts at injection point # 3 (box 5 in figure 5), which is located 890 meters below the tube of the tube reactor.
    [114] The preheater, which is the first of 13 tubes starting at 0 meters, and all reaction zones have an inner tube diameter of 5 centimeters. For all Examples and the Comparative Example, 100% of fresh ethylene and recycled ethylene are directed to the first reaction zone via, the first supply line in the reaction zone.
    [115] For all Examples and Comparative Examples, a mixture containing t-butyl-peroxy-2 ethylhexanoate (TBPO), di-t-butyl peroxide (DTBP), tert-butyl peroxypivalate (PIV) and a solvent iso-paraffinic hydrocarbon (boiling range> 179 ° C) is used as the initiator mixture for the first injection point. For injection points # 2 and # 3, a mixture containing only DTBP, TPO and the iso-paraffinic hydrocarbon solvent are used. Table 1 shows the flows of the peroxide initiator and solvent solution used for each of the Examples and the Comparative Example. Note that in order to maintain the reaction stability for the Examples at low reaction temperatures, or at peak temperatures below 290 ° C, the preceding peroxide mixture (source 11 in figure 6) must contain higher concentrations of TBPO and less PIV as shown in Table 1. TABLE 1

    [116] For all examples and comparative examples, 1-butene is used as CTA. The 1-butene is injected into the ethylene stream in the discharge drum of the first stage of the booster. The feed composition of the CTA to the process is adjusted between the Comparative Example and Example 1 - Example 6. This is done to control the melt index of the product. The 1-butene CTA is selected based on its ability to limit the molecular weight distribution of the final product when compared to other CTAs used in this technology.
    [117] For Example 1 - Example 6, peroxide injection # 2 (Source 12, in figure 5) is turned off, resulting in a two-peak reactor configuration. The peak temperatures for Example 1 - Example 6, for each of the two reaction zones are then decreased to reduce the total reactor temperature. The reduction in the total temperature of the reactor served to limit the distribution of molecular weight and to increase the density of the product, two properties that are key in relation to the properties of the film to finalize the use of this LDPE in a case as a shrink resin in which good optics and good rigidity, respectively, are important. The low temperature in the reactor coupled with the choice of CTA are both keys to the production of a product with high transparency, and limited molecular weight distribution with high density.
    [118] The process conditions in the tube reactor used for the manufacture of Comparative Examples 1 are given in Table 2. 6, and in Example

    [119] Note that in table 2 and figure 6, the BW 1 system goes to Zone 3, the BW 2 system goes to zones 4, 5, and 6 and the BW 3 system goes to Zone 1 and 2. A Figure 6 demonstrates that the temperature profile of the tube reactor shows the details of the Example 1 reactor and the reaction zones with respect to peroxide injections. The x-axis shows the junction between the tubes and the y-axis is the temperature for the reaction and for the boiling of water. Thermo couplings are used to measure the low reaction temperature in the tube during production. The reaction peaks for each zone are controlled by adjusting the flow of peroxide in each of the reaction zones. Peak temperatures are then used to control the product's molecular weight distribution and density. Characterization of Example 1 - Example 6 and Comparative Example 9
    [120] The characterization properties of the Example - Example 6 and Comparative Example 9 are illustrated in Table 3. From Table 3, the examples of this invention are generally lower in melting index, higher in density, larger at melting point , higher in heat of fusion, higher in crystallinity, higher in temperature of crystallization, comparable to or higher in resistance to melting, and higher in zero shear viscosity than the comparative example. The increased density is advantageous in terms of increased stiffness of this material in a film composition when the film needs to be rigid so that the film is cut, for example, to be used in a shrink film. The upper density also maintains the stiffness of the film when it is being dragged in a semi-molten state after passing through a shrink tunnel in one. Changes in thermal properties are, in many cases, a reflection of this high density. The lower melting index of these resins is very favorable in terms of the increased shrinkage stress in a resulting film the greater the melt strength and zero shear viscosity. TABLE 3

    [121] Table 4 illustrates the unsaturation properties of Examples 1 - Example 6 and Comparative Example 9. The Examples in general show slightly higher trans, similar to slightly lower vinyl levels, lower methyl levels, lower vinylidene levels, and lower carbonyl for the proportions of density in relation to the comparative example. TABLE 4

    [122] Table 5 shows the melt index, density, zero shear viscosity, and the TDGTPC properties of Example 1 - Example 6 and Comparative Example 1 - Comparative Example 19. For the results of TDGPC and zero shear viscosity , additional comparative examples were chosen to demonstrate the exclusivity of the Examples when compared to the Comparative Examples. These data are shown in Table 5 and punctuated in figure 7. As shown in figure 7, the examples of the invention demonstrate a unique relationship with Y = LSCDF3 and also with Mw / Mn. In particular, the examples of the invention have a much higher Y value than any of the comparative samples and in general have a lower Mw / Mn. The Y value is between about 0.4 and about 10. The unique structure as demonstrated by its high Y value of GPC-LS characterization of the embodiments of the invention is clearly shown in Table 5, where a large number of LDPE resins in range Similar MI is compared. The comparative examples in Table 5 cover an MI range from 0.17 to 0.87. The comparative examples in Table 5 also cover a wide range of branching levels with gpcBR values ranging from about 0.86 to about 2.02. The comparative examples in Table 5 also cover a wide range of molecular weights with cc-Mw values ranging from about 75,000 to about 140,000 g / mol. TABLE 5

    [123] Table 5 also shows the zero shear viscosities of the examples and comparative examples. The zero shear viscosity is organized versus the average molecular weight weight as determined through conventional calibration as shown in figure 8. The examples of this invention have a higher zero shear viscosity for a given average molecular weight when determined by conventional calibration. . This is advantageous in terms of improved shrinkage properties for the resins of the examples and in general, in the improved melt strength properties. As shown in figure 8, the examples of this invention are above a certain line by equation (18): Log (ηo, Pa-s, 190 ° C) = 12,333Log (ccGPCMw (g / mol)) - 56, 367 ( Eq. 18)
    [124] Where zero shear viscosity is obtained via a drag test at 190 ° C via the method described above, and the ccGPC Mw value is determined using the conventional GPC method also as described above. LDPE films:
    [125] The films of Example 1 - Example 6 and Comparative Example 9 are made in a 6 "mold with a screw of the LLDPE type. No internal bubble cooling was used. The parameters of the blowing film in general, used for producing the blowing film are shown in Table 6. Temperatures show temperatures close to the pellet hopper (Barrel 1) and in ascending order when the polymer is being extruded through the mold (melting temperature). of the film are shown in Table 7. The examples of the invention demonstrate a very low opacity, especially in Example 2, which has a material with an interior melting index, in this case, it usually makes it difficult to obtain a good opacity property. , the good optical properties of the films are reflected in the high brightness and transparency values.The examples of the invention demonstrate a low internal opacity, thus making it suitable for the layers internal structures of co-extruded structures to transmit good optical properties. The examples demonstrate good dart and piercing properties. The drying modulus values are generally high when compared to the comparative example.
    [126] Examples 1 and 3 demonstrate a very high percentage of CD retraction which is especially advantageous when this LDPE is used in a retractable interlayer film. The retraction stress values MD, as well as the retraction stress values CD are also very high in the examples of this invention, again reflecting an example of the utility of these retractable films. TABLE 6
    [127] Manufacturing conditions for the blowing / blown film for the samples of Example 1 - Example 6 and for Comparative Example 9, with results of the physical property shown in Table 7
    TABLE 7
    LDPE films in combination with LLDPE
    [128] LDPE and LLDPE mixtures were made and the films were blown from these mixtures. Table 8 shows two LLDPE resins used in these mixtures. Table 9 shows the two LDPE resins used in these mixtures, and Table 10 shows the 4 mixtures made from the resins in Table 8 and Table 9. TABLE 8

    [129] Mix 1 - mix 4 films are made in a 6 "mold with an LLDPE screw. No internal bubble cooling has been used. The blow film parameters in general used to produce the blow film are shown in Table 11. Temperatures show temperatures close to the pellet hopper (Barrel 1) and in ascending order when the polymer is being extruded through the mold (melting temperature). Table 12. Mix 2 and mix 4, each containing Example 1, when compared to mix 1 and mix 3, respectively, show good optics (low opacity, high gloss and transparency). The opacity of these samples is demonstrated in Figure 9 and the 45 degrees of brightness and transparency are shown in Figure 10. Figure 11 illustrates the improvements in the MD break and CD break of the inventive mixtures when compared to comparative mixtures.
    TABLE 12

    [130] All cited patents, testing procedures, and other documents, including priority documents, are fully incorporated by reference to the extent of said description are not inconsistent with this invention and for all purposes for which said incorporation is allowed.
    权利要求:
    Claims (17)
    [0001]
    1. Ethylene-based polymer, characterized by the fact that it has a density of 0.9 to 0.94 grams per cubic centimeter, a molecular weight distribution (Mw / Mn) of 4 to 10, a melting index (I2) from 0.05 to 0.8 grams for 10 minutes, measured according to ASTM D 1238, condition 190 ° C / 2.16 kg, a gpcBR value greater than 0.05, as determined by a gpcBR branch index and a Y value of GPC-LS characterization greater than 0.4, the Y value of GPC-LS characterization being determined according to the following formula: Y = Abs (A / B / (Abs (x) + (0 , 05)) where A is the area between (a) a straight line between a first point of intersection and a second point of intersection at two values of logarithmic cc-GPC molecular hair located on the curve of the normalized concentration-chromatogram LS, and (b) the curve of the concentration-normalized LS chromatogram between the two logarithmic cc-GPC molecular weight values, and where B is the area under the curve of the concentration-normalized LS chromatogram between two s logarithmic cc-GPC molecular weight values; and where x is determined according to the following formula:
    [0002]
    2. Polymer according to claim 1, characterized by the fact that the Y value is greater than 0.5.
    [0003]
    3. Polymer, according to claim 1, characterized by the fact that the melting index is less than 0.5 grams / 10 minutes.
    [0004]
    4. Ethylene-based polymer according to claim 1, characterized in that the molecular weight distribution (Mw / Mn) of the ethylene-based polymer composition is 4 to 6.
    [0005]
    5. Composition, characterized by the fact that it comprises the ethylene-based polymer, as defined in claim 1 and at least one other natural or synthetic polymer.
    [0006]
    6. Composition according to claim 5, characterized in that the synthetic polymer is selected from the group consisting of linear low density polyethylene (LLDPE), linear high density polyethylene (HDPE), and low density polyethylene (LDPE) .
    [0007]
    7. Composition according to claim 6, characterized in that the synthetic polymer comprises LLDPE.
    [0008]
    8. Composition according to claim 7, characterized in that the LLDPE comprises less than 50 weight percent of the composition.
    [0009]
    9. Film layer, characterized in that at least one film layer comprises the composition as defined in claim 7.
    [0010]
    10. Layer, according to claim 9, characterized by the fact that the film has an internal / surface opacity from 1.20 to 1.79.
    [0011]
    11. Ethylene-based polymer according to claim 1, characterized in that the polymer has a cc-GPC MW in g / mol and a zero (ηo) (Pa * s) log (ηo) shear viscosity ratio (Pa * s at 190 ° C))> 12.333 * log (cc-GPC Mw in g / mol) -56.367.
    [0012]
    12. Polymer, according to claim 11, characterized in that the melting index is less than 0.7 grams / 10 minutes.
    [0013]
    13. Polymer, according to claim 12, characterized by the fact that the log (ccGPC MW in g / mol) is greater than 4.88.
    [0014]
    14. Polymer according to claim 1, characterized in that the polymer has a melt resistance at 190 ° C in cN greater than 9cN.
    [0015]
    15. Film layer, characterized by the fact that it comprises the ethylene-based polymer, as defined in claim 1.
    [0016]
    16. Layer according to claim 15, characterized by the fact that the film layer has a contraction tension in the machine direction (MD) greater than 82.7 kPa (12 psi).
    [0017]
    17. Layer according to claim 15, characterized by the fact that the film has an internal / surface opacity of 1.81 to 2.67.
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    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-02-05| B06T| Formal requirements before examination|
    2019-05-28| B07A| Technical examination (opinion): publication of technical examination (opinion)|
    2019-10-29| B07A| Technical examination (opinion): publication of technical examination (opinion)|
    2020-07-14| B09A| Decision: intention to grant|
    2020-11-17| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 10 (DEZ) ANOS CONTADOS A PARTIR DE 17/11/2020, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US23252809P| true| 2009-08-10|2009-08-10|
    US61/232,528|2009-08-10|
    PCT/US2010/044389|WO2011019563A1|2009-08-10|2010-08-04|Ldpe for use as a blend component in shrinkage film applications|
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