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    • 专利摘要:
    COMPOSITIONS CONTAINING LOW DENSITY ETHYLENE-BASED POLYMERS WITH HIGH FUEL RESISTANCE AND FILMS FORMED THEREOF The invention provides a composition comprising the following: A) a first ethylene-based polymer formed by a high pressure polymerization process of free radicals and comprising the following properties: a) a ratio Mw (abs) versus 12: Mw ( abs ) A x [(I2) B], where A = 5.00 x 10(2) (kg/mole )/(dg/min)B and B = -0.40; and b) a MS versus I2 ratio: MS (Greater Equal) C x [(I2)D], where C = 13.5 cN/(dg/min) D and D = -0.55, c) an index of melting (I2) greater than 0.9 to 2.5 g /10 min; and B) a second ethylene-based polymer; and wherein the second ethylene-based polymer has a melt index (I 2 ) of 0.1 to 4.0 g/10 min.
    公开号:BR112015027619B1
    申请号:R112015027619-9
    申请日:2014-05-21
    公开日:2021-05-18
    发明作者:Teresa P. Karjala；Lori L. Kardos；Cornelis F. J. Den Doelder；Otto J. Berbee
    申请人:Dow Global Technologies Llc；
    IPC主号:
    专利说明:

    FUNDAMENTALS
    [001] Blown film production lines are typically limited in output by bubble stability. Blending Linear Low Density Polyethylene (LLDPE) with Low Density Polyethylene (LDPE) increases bubble stability, in part due to the greater melt strength of LDPE. The increase in melt strength, in part, predicts an increase in film production. However, also high melt strength can lead to poor quality gels and films, as well as potentially limiting the reduction capabilities for finer gauges. High melt strength resins also typically have reduced optics. Thus, there is a need for new compositions containing ethylene-based polymers, such as tubular LDPEs, that have an optimized balance of optical and mechanical melt strength properties for blown film applications.
    [002] The performance and application of films made from blends rich in LDPE with LDPE will be strongly influenced by the rheology, density and crystallinity of the selected LLDPE. The density and crystallinity of LLDPE can be varied over a wide range. The performance and application of films made from LDPE-rich blends with LLDPE will be increasingly influenced by the rheology and molecular topology of the selected LDPE.
    [003] The processability of the blend will, to a large extent, be determined by the rheological properties of the components of the LDPE blend. In contrast to LLDPE, the density and crystallinity levels of the LDPE resin can only be varied within narrow ranges. Furthermore, these narrow bands are, to a large extent, determined by the synthesis conditions necessary to achieve the desired molecular weight distribution (MWD) and the required rheological performance of LDPE. For blends rich in LDPE, the density and level of crystallinity may be slightly influenced by the type of LLDPE and/or the level of LLDPE allowed. The level of LLDPE allowed will depend on the processing performance required, for example bubble stability and bubble size. Improved rheological properties of the LDPE blend component will decrease the percentage of LDPE needed in the blend to achieve a given level of processing. Furthermore, a lower percentage of LDPE means that the contribution to film performance of the LLDPE blend component can be enhanced.
    [004] Improved rheological performance can be obtained by selecting LDPE resins with broad MWD and high melt strength. Typically LDPE resins with very broad MWD are prepared using autoclave-based reactor systems. The residence time distribution inherent in autoclave-based reactor systems leads to a wide MWD due to the differentiated growth paths (time) of the polymer molecules. The high melt strength of the autoclave mixing components is achieved by extremely broad and, in some cases, bimodal MWD. The ultra high molecular weight fraction present in autoclave, high melt strength resins complicates mixing on the molecular scale, could lead to gel formation in the resulting films, while negatively affecting the optical performance of the films.
    [005] A tubular reactor operated under typical process conditions, operates at higher conversion levels and lower production costs, produces "smaller MWD" resins than typical wide MWD resins of an autoclave train, such as those used for extrusion coating or in blends. As a result, more of the tubular resin of "Less MWD" must be blended with LLDPE to achieve certain processing performance of LDPE/LLDPE blends, or a lower target melt index must be selected for LDPE. Lower MI will negatively affect processing capacity, such as increased processing pressures.
    [006] Thus, there continues to be a need for new compositions containing LDPE, which can increase the melt strength and processing performance of LDPE/LLDPE blends, and which can be prepared with low conversion costs in a tubular process. Furthermore, there is a need for such compositions with improved processing performance (maximum in-line speed and/or large bubble operation) and/or film properties (mechanical and reduction performance and/or optical appearance). This requires LDPE resins made with lower melt index, high melt strength, and very broad MWD, but without the ultra high molecular weight fraction of "wide MWD" autoclave resins, and which can be made in a tubular process.
    [007] Uniform residence time in tubular reactors leads to narrower MWD, therefore, very wide MWD can only be achieved in tubular reactors through extremely differentiated application polymerization conditions, for example, as described in International Publication W02013/ 078018, and/or application for a branching/crosslinking agent, for example, as described in US7820776. These tubular polyethylenes will have a specific composition (eg density) and functionality as determined by the applied process conditions, the type and level of branching agent and/or comonomer. Undesirable gels in the polymer can be a problem, resulting from the use of branching or crosslinking agents.
    [008] Low density polyethylenes and blends are disclosed in the following: publication US 2014/0094583 Publication; US Patent 5,741,861; US Patent 7,741,415; US Patent 4,511,609; US Patent 4,705,829; publication US 2008/0038533; JP61-241339 (Abstract); JP2005-232227 (Abstract); and International Publications No. W02010/144784, W02011/019563, WO 2010/042390, WO 2010/144784, WO 2012/082393, WO 2006/049783, WO 2009/114661, US 2008/0125553, EP0792318A1 and EP 2239283B1. However, such polymers do not provide an optimal balance of high melt strength and improved mechanical film properties for blown film applications. Thus, as discussed above, there continues to be a need for new ethylene-based polymer compositions that have an optimized balance of melt strength, optics, processability and yield, and hardness. These and other needs were met by the following invention. SUMMARY OF THE INVENTION
    [009] The invention provides a composition comprising the following;
    [010] [A) a first ethylene-based polymer, formed by a free-radical, high-pressure polymerization process, and comprising the following properties: a) a Mw(abs) versus 12 ratio: Mw(abs) < A x where A = 5.00 x 102 (kg/mole)/(dg/min)B and B = - 0.40, and b) an MS versus 12 ratio: MS C x [(I2)°], in that C = 13.5 cN/(dg/min)° and D = -0.55, c) a melt index (12) greater than 0.9 at 2.5 g/10 min; and
    [011] B) a second ethylene-based polymer; and
    [012] wherein the second ethylene-based polymer has a melt index (I2) from 0.1 to 4.0 g/10 min.
    [013] BRIEF DESCRIPTION OF THE DRAWINGS
    [014] Figure 1 is a polymerization flow diagram.
    [015] Figure 2 represents the maximum production in the blown film line described here in relation to the % of LDPE in LLDPE1 used in the film.
    [016] Figure 3 represents the MD shrinkage stress measured on a film prepared at a maximum rate versus the LDPE% in LLDPE1 used in the film. DETAILED DESCRIPTION
    [017] As discussed above, the invention provides a composition comprising the following:
    [018] A) a first ethylene-based polymer, formed by a free radical polymerization process at high pressure, and comprising the following properties: a) a ratio of Mw(abs) versus 12: Mw(aba) < A x where A = 5.00 x 102 (kg/mole)/(dg/min)B, and B = -0.40, b) an MS versus 12 ratio: MS C x [(I2)°], where C = 13.5 cN/(dg/min)° and D = -0.55, c) a melt index (I 2 ) greater than 0.9 at 2.5 g/10 min; and
    [019] B) a second ethylene-based polymer; and
    [020] wherein the second ethylene-based polymer has a melt index (I2) of 0.1 to 4.0 g/10 min.
    [021] The composition may comprise a combination of two or more modalities described herein.
    [022] The first ethylene-based polymer may comprise a combination of two or more modalities as described herein.
    [023] The second ethylene-based polymer may comprise a combination of two or more modalities as described herein.
    [024] In characteristic a) above, the MW(abs), is determined by GPC, as described here.
    [025] In characteristic b) above, the Melting Strength (MS) is determined at 190°C; see test method described here.
    [026] [In one embodiment, the second ethylene-based polymer has a melt index (I2) from 0.2 to 3.5 g/10 min, further from 0.3 to 3.0 g/10 min , still from 0.4 to 2.5 g/10 min.
    [027] In one embodiment, the second ethylene-based polymer has a density of 0.870 to 0.969 g/cc, still 0.890 to 0.950 g/cc, still 0.910 to 0.940 g/cc, still 0.915 to 0.930 g/cc .
    [028] In one embodiment, the second ethylene-based polymer is present in an amount of 5 to 95 percent by weight, further from 10 to 95 percent by weight, still from 20 to 95 percent by weight, still from 30 to 95 percent by weight, based on the weight of the composition.
    [029] In one embodiment, the second ethylene-based polymer is present in an amount of 40 to 95 percent by weight, still from 50 to 95 percent by weight, still from 60 to 95 percent by weight, still from 70 to 95 percent by weight, based on the weight of the composition.
    [030] In one embodiment, the second ethylene-based polymer is an ethylene/α-olefin interpolymer, and still a copolymer. In another embodiment, the ethylene/α-olefin copolymer is a heterogeneously branched ethylene/α-olefin interpolymer, and further a copolymer. Suitable alpha-olefins include, among others, propylene, butene-1, pentene-1, 4-methylpentene-1, pentene-1, hexene-1 and octene-1, and preferably propylene, butene-1, hexene-1 and octene -1.
    [031] In one embodiment, the second ethylene-based polymer is selected from an ethylene/alpha-olefin copolymer, a low density polyethylene (LDPE), a high density polyethylene (HDPE), or a combination thereof .
    [032] The second ethylene-based polymer may comprise a combination of two or more modalities as described herein.
    [033] In one embodiment, the first ethylene-based polymer is present in an amount from "greater than zero" to 30 percent by weight, further from 1 to 25% by weight, further from 2 to 20% by weight , based on the sum of the weight of the first ethylene-based polymer and the second ethylene-based polymer.
    [034] In one embodiment, the first ethylene-based polymer is present in an amount greater than or equal to 20 percent by weight, even greater than or equal to 50 percent by weight, based on the sum. of the weight of the first ethylene-based polymer and the second ethylene-based polymer.
    [035] In one embodiment, the first ethylene-based polymer is present in an amount of from 1 to 95 percent by weight, further from 5 to 95 percent by weight, further from 10 to 90 percent by weight, based on the sum. of the weight of the first ethylene-based polymer and the second ethylene-based polymer.
    [036] In one embodiment, the first ethylene-based polymer has a melt index (I2) from 0.9 g/10 min to 2.2 g/10 min, further from 0.9 g/10 min to 2.0 g/10 min (ASTM 1238 2.16 kg/190°C).
    [037] In one embodiment, the first ethylene-based polymer has b) a ratio Mw(abs) versus 12: Mw(abs) < A x where A = 4.25 x 102 (kg/mole)/(dg/ min)B, and B = -0.40 (Mw(abs) by GPC).
    [038] In one embodiment, the first ethylene-based polymer has b) a ratio Mw(abs) versus 12: Mw(abs) < A x where A = 3.50 x 102 (kg/mole)/(dg/ min)B, and B = -0.40 (Mw(abs) by GPC).
    [039] In one embodiment, the first ethylene-based polymer has c) a MS versus 12: MS C x [(I2)°] ratio, where C = 14.5 cN/(dg/min)°, and D = -0.55 (Stress resistance = MS, 190°C)
    [040] In one embodiment, the first ethylene-based polymer has c) a MS versus 12: MS.>.- C x [(I2)°] ratio, where C = 15.5 cN/(dg/min) °, and D = -0.55 (Stress resistance = MS, 190°C)
    [041] In one embodiment, the first ethylene-based polymer has a G' value greater than or equal to 140 Pa at 170°C, even greater than or equal to 150 Pa, at 170°C, even greater than that or equal to 160 Pa at 170°C.
    [042] In one embodiment, the first ethylene-based polymer has a melt strength greater than or equal to 9.0 cN at 190°C, even greater than or equal to 12.0 cN, at 190°C, even greater than or equal to 15.0 cN at 190°C.
    [043] In one embodiment, the first ethylene-based polymer has a Melt Strength (190°C) of 10 to 20 cN.
    [044] In one embodiment, the first ethylene-based polymer has a "weight fraction (w) of molecular weight greater than 106 g/mol, based on the total polymer weight, as determined by GPC(abs), which satisfies the following relationship: w <E x [(12)F], where E = 0.110 (dg/min)-F and F = -0.38 (GPC).
    [045] In one embodiment, the first ethylene-based polymer is polymerized in at least one tubular reactor. In another embodiment, the first ethylene-based polymer is polymerized in a tubular reactor system, which does not comprise an autoclave reactor.
    [046] In one embodiment, the first ethylene-based polymer is polymerized in a reactor configuration comprising at least one tubular reactor.
    [047] In one embodiment, the first ethylene-based polymer is an LDPE.
    [048] In one embodiment, the first ethylene-based polymer is selected from a polyethylene homopolymer or an ethylene-based interpolymer.
    [049] In one embodiment, the first ethylene-based polymer is selected from a polyethylene homopolymer or an ethylene-based copolymer; and wherein the ethylene-based copolymer comonomer is selected from a vinyl acetate, an alkyl acrylate, carbon monoxide, an acrylic acid, a carboxylic acid containing comonomer, an ionomer, a mono-olefin, or selected from of a vinyl acetate, an alkyl acrylate, acrylic acid, or a mono-olefin. In another embodiment, the comonomer is present in an amount of 0.5 to 30% by weight of comonomer, based on the weight of copolymer.
    [050] In one embodiment, the first ethylene-based polymer has a density from 0.910 to 0.940 g/cc, still from 0.912 to 0.935 g/cc, still from 0.914 to 0.930 g/cc (1 cc = 1 cm3) .
    [051] In one embodiment, the first ethylene-based polymer has a density of 0.910-0.930 g/cc, further from 0.912 to 0.925 g/cc, further from 0.914 to 0.920 g/cc (1 cc = 1 cm3).
    [052] In one embodiment, the first ethylene-based polymer has a density greater than or equal to 0.914 g/cc, or greater than or equal to 0.916 g/cc.
    [053] The first ethylene-based polymer may comprise a combination of two or more modalities as described herein.
    [054] In one embodiment, when a composition of the invention is formed into a film, through a blown film process, the maximum production rate is at least 15 percent greater than the maximum production rate of a similarly formed film from a similar composition, except that the composition contains 100% by weight of the second ethylene-based polymer, based on the sum of the weight of the first ethylene-based polymer and the second ethylene-based polymer.
    [055] A composition of the invention may comprise a combination of two or more modalities as described herein.
    [056] The invention also provides an article comprising at least one component formed from a composition of the invention.
    [057] In one modality, the article is selected from coatings, films, foams, laminates, fibers or tapes. In another modality, the article is a movie.
    [058] The invention also provides a film comprising at least one layer formed from a composition of the invention.
    [059] In one embodiment, the film includes at least two layers.
    [060] In one embodiment, the film has an MD shrinkage stress greater than 5.00 psi.
    [061] An article of the invention may comprise a combination of two or more modalities as described herein.
    [062] A film of the invention may comprise a combination of two or more modalities as described herein. Polymerizations
    [063] For a high pressure, free radical initiated polymerization process, two basic types of reactors are known. The first type is an agitated autoclave vessel with one or more reaction zones (autoclave reactor). The second type is a jacketed tube, which has one or more reaction zones (tubular reactor). The pressure in each autoclave and tubular reactor zone of the process is typically from 100 to 400, more typically from 120 to 360, and still typically from 150 to 320 MPa. The polymerization temperature in each tubular reactor zone of the process is typically from 100 to 400, more typically from 130 to 360, and still typically from 140 to 330°C.
    [064] The polymerization temperature in each zone of the process autoclave reactor is typically from 150 to 300, more typically from 165 to 290, and even more typically from 180 to 280°C.
    [065] The first ethylene-based polymers with broad MWD are typically prepared under polymerization conditions that comprise one or more of the following process elements: • Reduction of operating pressure (versus maximum operating pressure of the reactor system); • High polymerization temperatures: one or more autoclave zone and/or one or more tube reactor zone are operated at a maximum peak or control temperature exceeding, respectively 240 and 290°C; • Minimum of three autoclave reaction zones and/or tubular nature; • Selection of CTA type and/or distribution over reaction zones to ensure wide MWD product; and/or • Optional use of a bifunctional coupling and/or branching agent.
    [066] The high pressure process of the present invention, for the production of polyethylene homopolymers or ethylene-based interpolymers having the advantageous properties as found in accordance with the invention, is preferably carried out in a tubular reactor having at least three zones of reaction. Initiators
    [067] The process of the present invention is a free radical polymerization process. The type of free radical initiator to be used in the present process is not critical, but preferably one of the applied initiators should allow high temperature operation in the range from 300°C to 350°C. Free radical initiators that are commonly used include organic peroxides such as peresters, perketals, peroxy ketones, percarbonates, and multifunctional cyclic peroxides. These organic peroxy initiators are used in conventional amounts, typically from 0.005 to 0.2% by weight based on the weight of polymerizable monomers. Other suitable initiators include azodicarboxylic esters, azodicarboxylic dinitriles and 1,1,2,2-tetramethyleneethane derivatives, and other components capable of forming free radicals in the desired operating temperature range.
    [068] Peroxides are typically injected in the form of diluted solutions in a suitable solvent, for example, in a hydrocarbon solvent. In one embodiment, an initiator is added to at least one polymerization reaction zone, and wherein the initiator has a "half-life temperature in one second" greater than 255°C, preferably greater than 260°C . In another embodiment, such initiators are used at a peak polymerization temperature of 320°C to 350°C. In another embodiment, the initiator comprises at least one peroxide group incorporated into a ring structure.
    [069] Examples of such initiators include, among others, TRIGONOX 301 (3,6,9-triethyl-3,6,9-trimethyl-1,4,7 triperoxonean) and TRIGONOX 311 (3,3,5,7, 7-pentamethyl-1,2,4-trioxepane), both available from Akzo Nobel, and HMCH-4-AL(3,3,6,6,9,9-hexamethyl-1,2,4,5- tetroxonan) available from United Initators. See also International Publications WO 02/14379 and WO 01/68723. Chain Transfer Agents (CTA)
    [070] Chain transfer agents or telogens are used to control the melt index in a polymerization process. Chain transfer involves the termination of growing polymer chains, thus limiting the ultimate molecular weight of the polymer material. Chain transfer agents are typically hydrogen atom donors that react with a growing polymer chain and stop the polymerization chain reaction. These agents can be of many different types, from saturated or unsaturated hydrocarbons to aldehydes, ketones or alcohols. By controlling the concentration of the selected chain transfer agent, one can control the length of the polymer chains, and therefore the molecular weight, eg the number average molecular weight, Mn. The melt flow index (MFI or 12) of a polymer, which is related to Mn, is controlled in the same way.
    [071] The chain transfer agents used in the process of the present invention include, among others, aliphatic and olefinic hydrocarbons, such as pentane, hexane, cyclohexane, propene, pentene or hexane; ketones such as acetone, diethyl ketone or diamyl ketone; aldehydes such as formaldehyde or acetaldehyde; and saturated aliphatic aldehyde alcohols such as methanol, ethanol, propanol or butanol. The chain transfer agent can also be a monomeric chain transfer agent. For example, see WO 2012/057975, W02013/095969, and W02014/003837.
    [072] Differentiated CTA concentrations in the reaction zones can be used to achieve and control the desired molecular weight distribution. Means to differentiate the concentration of CTA in reaction zones include, among others, methods described in W02013/059.042, W02011/075465 and
    [073] W02012/044504.
    [074] Another way to influence the melt index includes the elaboration and control, in the ethylene recycle streams, of incoming ethylene impurities, such as methane and ethane, peroxide dissociation products, such as tert butanol, acetone, etc., and/or solvent components used to dilute the initiators. These ethylene impurities, peroxide dissociation products and/or diluting solvent components can act as chain transfer agents. Monomers and Comonomers
    [075] The term ethylene interpolymer as used in the present description and in the claims refers to ethylene polymers and one or more comonomers. Suitable comonomers for use in the ethylene polymers of the present invention include, among others, ethylenically unsaturated monomers and, especially, C3_20 alpha-olefins, carbon monoxide, vinyl acetate, alkyl acrylates, or a higher functional or bifunctional comonomer (includes monomers with two or more monomeric groups). Usually comonomers can also act as chain transfer agents to some degree. These comonomers with high chain transfer activity are termed monomeric CTAs. Additions
    [076] A composition of the invention may comprise one or more additives. Suitable additives include stabilizers; fillers, such as organic or inorganic particles, including clays, talc, titanium dioxide, zeolites, powdered metals, organic or inorganic fibers, including carbon fibers, silicon nitride fibers, steel or mesh wires, and strands of nylon or polyester, nano-sized particles, clays, and so on; thickeners, thinners, including paraffinic oil or naphthalene oils. A composition of the invention can comprise other types of polymers. applications
    [077] The polymers of the present invention can be employed in a variety of conventional thermoplastic manufacturing processes to produce useful articles, including, but not limited to, monolayer and multilayer films; molded articles, such as blow molded, injection molded, or rotational molded articles; coatings; fibers; and woven or non-woven.
    [078] A polymer of the invention can be used in a variety of films, including, but not limited to, extrusion coating, food packaging, consumer, industrial, agricultural (applications or films), laminating films, films that produce fresh cuts, meat films, cheese films, candy films, reducing whitening films, reducing films for gluing, stretching films, silage films, kiln films, fumigation films, liner films, stretch covers, heavy transport bags , pet food, sandwich bags, sealants and diaper backsheets.
    [079] A polymer of the invention is also useful in other direct end use applications. A polymer of the invention can be used for wire and cable coating operations, in sheet extrusion for vacuum forming operations, and forming of molded articles, including the use of injection molding, blow molding processes or processes rotational molding.
    [080] Other suitable applications for the polymers of the invention include elastic films and fibers; soft-touch goods such as appliance handles; joints and cutouts; interior parts of records and clippings; foam products (both open and closed cell); impact modifiers for other thermoplastic polymers, such as high density polyethylene, or other olefin polymers; cover coatings; and floor. DEFINITIONS
    [081] Unless otherwise indicated, implied from the context, or customary in the art, all parts and percentages are based on weight and all test methods are current as of the filing date of the present disclosure.
    [082] The term "composition" as used herein, refers to a mixture of materials that comprise the composition, as well as the reaction products and decomposition products formed from the materials of the composition.
    [083] The terms "blend" or "polymer blend", as used, means an intimate physical blend (ie, no reaction) of two or more polymers. A mixture may or may not be miscible (not phased at the molecular level). The mixture may or may not be separated into phases. A mixture may or may not contain one or more domain configurations, as determined from transmission electronic spectroscopy, light scattering, X-ray scattering, and other methods known in the art. Mixing can be accomplished by physically mixing the two or more polymers at the macro level (for example, melting mixed or manipulated resins) or at the micro level (for example, simultaneous formation in the same reactor, or formation of one polymer in the presence of another polymer).
    [084] The term "polymer" refers to a compound prepared by polymerizing monomers, the same or a different type. The generic term polymer thus encompasses the term homopolymer (which refers to polymers prepared from only one type of monomer, with the understanding that trace amounts of impurities can be incorporated into the polymer structure), and the term "interpolymer", as defined below. Trace amounts of impurities can be incorporated into and/or within a polymer.
    [085] The term "interpolymer" refers to polymers prepared by polymerizing at least two different types of monomers. The generic term interpolymer includes copolymers (which refers to polymers made from two different monomers), and polymers made from greater than two different types of monomers.
    [086] The term "ethylene-based polymer" or "ethylene polymer" refers to a polymer that comprises a major amount of polymerized ethylene, based on the weight of the polymer, and optionally may comprise at least one comonomer.
    [087] The term "ethylene-based interpolymer" or "ethylene interpolymer" refers to an interpolymer that comprises a major amount of polymerized ethylene, based on the weight of the interpolymer, and comprises at least one comonomer.
    [088] The term "ethylene-based copolymer" or "ethylene-based copolymer" refers to a copolymer comprising a major amount of polymerized ethylene based on the weight of the copolymer, and only one comonomer (thus only two types of monomers).
    [089] The terms "autoclave-based products" or "autoclave-based polymers", as used herein, refer to polymers prepared in a reactor system comprising at least one autoclave reactor.
    [090] The phrase "high pressure free radical polymerization process", as used herein, refers to a free radical initiated polymerization carried out at an elevated pressure of at least 1000 bar (100 MPa).
    [091] The terms "comprising", "including", "having", and derivatives thereof, are not intended to exclude the presence of any component, or additional step or process, whether or not the same is specifically disclosed. For the avoidance of doubt, all compositions claimed by the use of the term "comprising" may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless otherwise indicated. In contrast, the term, "consisting essentially of" excludes from its scope any mention following any other component, step or procedure, with the exception of those which are not essential to operability. The term "consisting of" excludes any component, step or procedure not specifically delineated or listed. TEST METHODS
    [092] Density: Samples for density measurement are prepared in accordance with ASTM D 1928. Polymer samples are pressed at 190°C and 30,000 psi (207 MPa) for three minutes, then at 21 °C and 207 MPa for one minute. Measurements are made within one hour of sample pressing using ASTM D792, Method B.
    [093] Melt Index: Melt Index, or 12 (or 12), (grams/10 minutes or dg/min) is measured according to ASTM D 1238, Condition 190°C/2.16 kg. In is measured to ASTM D 1238, Condition 190°C/10 kg.
    [094] Triple Detector Gel Permeation Chromatography (TDGPC): high temperature 3Det-GPC analysis is performed on an ALLIANCE GPCV2000 instrument (Waters Corp.), set at 145°C. The flow rate for the GPC is 1 mL/min. The injection volume is 218.5 pL. The column set consists of four Mixed-A columns (20 µm particles, 7.5 x 300 mm; Polymer Laboratories Ltd).
    [095] Detection can be achieved through the use of a PolymerChAR IR4 detector, equipped with a CH sensor; a Wyatt Technology Dawn DSP MALS detector (Wyatt Technology Corp., Santa Barbara, CA, USA), equipped with a 30 mW argon ion laser operating at À =488 nm; and a Waters tri-pillar viscosity detector. The MALS detector is calibrated by measuring the dispersion intensity of the TCB solvent. The normalization of the photodiodes is done by injection of SRM 1483, a high density polyethylene with a weight average molecular weight (Mw) of 32,100 g/mol and polydispersity (MWD) of 1.11. A specific refractive index (dn/dc) increment of -0.104 mL/mg for polyethylene in TCB is used.
    [096] Conventional GPC calibration is done with 20 narrow PS standards (Polymer Laboratories Ltd.) with molecular weights in the range of 580 to 7,500,000 g/mol. The standard peak polystyrene molecular weights are converted to polyethylene molecular weights from the following equation: Polyethylene = AX (Polystyrene)B with A = 0.39, B = 1. The value of A is determined using a linear homopolymer of high density polyethylene (HDPE) with a MW of 115,000 g/mol. HDPE reference material is also used to calibrate the IR detector and viscometer assuming 100% mass recovery and an intrinsic viscosity of 1.873 dL/g.
    [097] The column calibration curve was obtained by fitting a first-order polynomial for the respective polyethylene equivalent calibration points obtained from the above equation, for the observed elution volumes.
    [098] Numerical, weight and Z average molecular weights (GPC) were calculated according to the following equations:
    where, 1.11; is the weight fraction of component i° and Mi is the molecular weight of component i°. *The molecular weight distribution (MWD) was expressed as the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn).
    [099] Grade "Analyzed Baker" 1,2,4-trichlorobenzene distillate (JT Baker, Deventer, Netherlands), containing 200 ppm 2,6-di-tert-butyl-4-methylphenol (Merck, Hohenbrunn, Germany ), is used as the solvent for sample preparation as well as for the 3Det-GPC experiment. HDPE SRM 1483 is obtained from the US National Institute of Standards and Technology (Gaithersburg, MD, USA). [100] LDPE solutions are prepared by dissolving the samples, under gentle agitation, for three hours at 160°C. PS standards are dissolved under the same conditions for 30 minutes. The sample concentration for the 3Det-GPC experiment is 1.5 mg/mL, and the polystyrene concentrations are 0.2 mg/mL. [101] A MALS detector measures the scattered signal from polymers or particles in a sample under different scatter angles e. The basic light scattering equation (from M. Anderson, B. Wittgren, K.-G. Wahlund, Anal. Chem. 75, 4279 (2003)) can be written as follows:
    where Ro is the excess Rayleigh ratio, K is an optical constant which, among other things, is dependent on the increment of the specific refractive index (dn/dc), c is the solute concentration, M is the molecular weight, Rg is the radius of rotation and Á is the wavelength of the incident light. Calculating the molecular weight and radius of rotation from the light scattering data requires extrapolation to the zero angle (see also PJ Wyatt, Anal. Chim. Acta 272, 1 (1993)). This is done through the graph (Kc/R0)'' as a function of sin2(0/2) in the so-called Debye graph. The molecular weight can be calculated from the intersection with the ordinate, and the radius of rotation from the initial slope of the curve. The second virial coefficient is considered insignificant. Intrinsic viscosity numbers are calculated from both the viscosity and concentration detector signals by taking the ratio of the specific viscosity to the concentration in each elution slice. [102] ASTRA 4.72 software (Wyatt Technology Corp.) is used to collect the signals from the IR detector, viscometer, and MALS detector, and to perform the calculations. [103] Calculated molecular weights, eg MW(abs) and molecular weight distributions (eg Mw(abs)/Mn(abs)) are obtained using a light scattering constant derived from one or more of the polyethylene standards mentioned and a refractive index concentration coefficient, dn/dc, of 0.104. Generally, the mass detector response and light scattering constant should be determined from a linear standard with a molecular weight greater than about 50,000 Daltons. Calibration of the viscometer can be performed using the methods described by the manufacturer, or alternatively, using published values of suitable linear standards, such as 1475a, 1482a, 1483, or 1484a reference standard materials (SRM). Chromatographic concentrations are assumed to be low enough to eliminate the targeting of 2nd virial coefficient effects (concentration effects on molecular weight). [104] The MWD(abs) curve obtained from TD-GPC is summarized with three characteristic parameters: Mw(abs), Mn(abs), and w, where w is defined as "weight fraction of molecular weight greater than 106 g/mole, based on total polymer weight, and as determined by GPC(abs)". [105] In equation form, the parameters are determined as follows. Numerical integration from the table of "logM" and "dw/dlogM" is usually done with the trapezoidal rule:
    G' Rheological [106] The sample used in the measurement of G' was prepared from a compression molding plate. A piece of aluminum foil was placed on a backing plate, and a template or matrix was placed on top of the backing plate. About 12 grams of resin were placed in the matrix, and a second piece of aluminum foil was placed over the resin and matrix. A second backing plate was then placed on top of the aluminum sheet. The whole assembly was then placed in a compression molding press, which was run under the following conditions: 3 min at 150°C, at 10 bar pressure, followed by 1 min at 150°C, at 150 bar, followed by a "1.5 min" quench cooldown to room temperature at 150 bar. A 25 mm disc was removed from the compression molded plate. The thickness of this disc was approximately 2.0 mm. [107] The rheology measurement to determine G' was made in a nitrogen environment at 170°C and a strain of 10%. The removed disc was placed between the two parallel "25 mm" plates located in an ARES-1 rheometer oven (Rheometrics SC), which was preheated for at least 30 minutes at 170°C, and the gap of the parallel plates of "25 mm" was slowly reduced to 1.65 mm. The sample was then allowed to continue for exactly 5 minutes under these conditions. The oven was then opened, the excess sample was carefully cut around the edge of the plates, and the oven was closed. The sample's storage modulus and loss modulus were measured using a small amplitude, oscillatory shear, according to a decreasing frequency sweep of 100 to 0.1 rad/s (when able to obtain a G" value smaller than the than 500 Pa at 0.1 rad/s), or from 100 to 0.01 rad/s. For each frequency sweep, 10 points (logarithmically spaced) per frequency decade were used. [108] The data were plotted (G' (Y-axis) versus G" (X-axis)) on a log-log scale. The Y-axis scale covered the range from 10 to 1000 Pa, while the X-axis scale covered the range from 100 to 1000 Pa. Orchestrator software was used to select the data in the region where G" was between 200 and 800 Pa ( or using at least 4 data points). Data were fitted to a log polynomial model using the fit equation Y = C1+C2 ln(x). Using Orchestrator software, G' to G" equal to 500 Pa was determined by interpolation. [109] In some cases, the G' (in a G" of 500 Pa) was determined from test temperatures of 150°C and 190°C. The value at 170°C was calculated from an interpolation linear from the values for these two temperatures Melting resistance [110] Melting resistance measurements are performed on a Göettfert Rheotens 71.97 (Göettfert Inc.; Rock Hill, SC) connected to a Göettfert Rheotester 2000 capillary rheometer. molten polymer is extruded through a capillary matrix with a flat entry angle (180 degrees) with a capillary diameter of 2.0 mm and an aspect ratio (capillary length/capillary diameter) of 15. [111] After balancing the samples at 190°C for 10 minutes, the piston is run at a constant piston speed 0.265 mm/sec. The standard test temperature is 190°C. The sample is taken uniaxially to a set of acceleration clamps located 100 mm below the matrix with an acceleration of 2.4 mm/second 2. The tensile force is recorded as a function of the pickup speed of the pinch rollers. Fusion resistance is reported as the plateau force (cN) of the strand to break. The following conditions are used in the melt strength measurements: piston speed = 0.265 mm/second; wheel acceleration = 2.4 mm/s2; capillary diameter = 2.0 mm; capillary length = 30 mm; and cylinder diameter = 12 mm. Nuclear Magnetic Resonance (13C NMR) [112] Samples were prepared by adding approximately 0.3 g of a 50/50 mixture of tetrachloroethane-d2/orthodichlorobenzene, containing 0.025 M Cr(AcAc)3" to a sample of "0 .25 to 0.40 g polymer" in a 10 mm NMR tube. Oxygen was removed from the sample by placing the tubes open in a nitrogen environment for at least 45 minutes. The samples were then homogenized and dissolved by heating of the tube, and its contents to 150°C, using a heat block and heat gun. Each dissolved sample was visually inspected to ensure homogeneity. The samples were thoroughly mixed, immediately prior to analysis, and were not allowed to cool beforehand. of insertion into heated NMR sample holder.[113] All data were collected using a Bruker 400 MHz spectrometer. 90 degree eta, and reverse port decoupling, with a sample temperature of 125°C. All measurements were made on samples that did not rotate in locked mode. Samples were allowed to thermally equilibrate for seven minutes prior to data acquisition. Chemical shifts of 13c NMR were referenced internally to the EEE triad at 30.0 ppm. The C6+ value was a direct measure of C6+ branches in LDPE, where the long branches were not distinguished from the ends of the chain. The 32.2 ppm peak, which represents the third carbon from the end of all chains or branches of six or more carbons, was used to determine the C6+ value. Nuclear Magnetic Resonance (1H NMR). Sample Preparation [114] Samples were prepared by adding approximately 130 mg of sample to "3.25 g of 50/50, by weight, tetrachloroethane-d2/perchlorethylene" with 0.001 M Cr(AcAc)3 in an NMR tube NORELL 1001-7, 10 mm. Samples were purged by bubbling N2 through the solvent, using a pipette inserted into the tube, for about five minutes to avoid oxidation. Each tube was capped, sealed with TEFLON tape, and then soaked at room temperature overnight to facilitate sample dissolution. Samples were kept in an N2 purge box during storage, before, and after preparation, to minimize exposure to OC. Samples were heated and stirred at 115 °C to ensure homogeneity. Data Acquisition Parameters [115] 1H NMR was performed on a Bruker AVANCE 400 MHz spectrometer, equipped WITH a Bruker Dual DUL high temperature CryoProbe, and a sample temperature of 120°C. Two experiments were performed to obtain the spectra, a control spectrum to quantify total polymer protons, and a double pre-saturation experiment, which suppressed the intense polymer backbone peaks, and allowed high-sensitivity spectra for quantification. of the end groups. Control was performed with ZG pulse, 4 scans, SWH 10,000 Hz, AQ 1.64s, Dl 14s. The double presaturation experiment was performed with a modified pulse sequence, TD 32768, 100 scans, DS 4, SWH 10,000 Hz, AQ 1.64s, Dl is, D13 13s. Data Analysis - 1H NMR Calculations [116] The residual 1H signal in the TCE-D2 (at 6.0 ppm) was integrated, and adjusted to a value of 100, and the integral from 3 to -0.5 ppm was used as the entire polymer signal in the control experiment. For the pre-saturation experiment, the TCE signal was also set to 100, and the corresponding integrals for unsaturation (vinylene at about 5.40 to 5.60 ppm, trisubstituted at about 5.16 to 5.35 ppm , vinyl at about 4.95 to 5.15 ppm, and vinylidene at about 4.70 to 4.90 ppm) were obtained. [117] In the spectrum of the pre-saturation experiment, the regions for cis and trans-vinylene, trisubstituted, vinyl and vinylidene were integrated. The integral of the entire polymer from the control experiment was divided by two to obtain a value that represents X thousands of carbon atoms (that is, if the polymer integral = 28000, this represents 14,000 carbon atoms, and X = 14). [118] The unsaturated group integrals, divided by the corresponding number of protons that contribute to the integral, represent the moles of each type of unsaturation per X thousand carbons. Dividing the moles of each type of unsaturation by X then generates moles of unsaturated groups per 1000 moles of carbon atoms. Film Test [119] The following physical properties were measured on films as described in the experimental section. Film thickness was measured using a Measuretech instrument. [120] Total Opacity (Overall) and Inner Opacity: Inner opacity and total opacity were measured according to ASTM D 1003-07. Internal opacity was obtained by matching refractive index using mineral oil (1-2 teaspoons), which was applied as a coating over each surface of the film. A Hazegard Plus (BYK-Gardner USA; Columbia, MD) was used for the test. For each test, [121] five samples were examined, and one mean reported. Sample dimensions were "6" x 6". [122] 45° Brightness: ASTM D2457-08 (average of five film samples; each sample "10" x 10"). [123] Clarity: ASTM D1746-09 (average of five film samples; each sample "10" x 10"). [124] Secant Modulus 2% - MD (Machine Direction) and CD (Cross Direction): ASTM D882-10 (average of five film samples in each direction; each sample "1 in x 6 in"). [125] Elmendorf MD and CD Burst Strength: ASTM D1922-09 (average of 15 film samples in each direction; each sample "3" x 2.5" half moon shape). [126] MD and CD Tensile Strength: ASTM D882-10 (average of five film samples in each direction; each sample "1 in x 6 in"). [127] Dart Impact Resistance: ASTM D1709-09 (minimum 20 drops to achieve 50% failure, typically ten "10" x 36" strips). [128] Puncture Strength: Puncture was measured on an INSTRON Model 4201 with SINTECH TESTWORKS SOFTWARE version 3.10. The sample size was "6" x 6" and four measurements were taken to determine an average punch value. The film was conditioned for 40 hours after film production, and for at least 24 hours in a controlled ASTM laboratory (23°C and 50% relative humidity). A "100-pound" load cell was used with a 4-inch diameter round sample holder. The drill probe is a “1/2 inch diameter” polished stainless steel ball (on a 2.5” rod) with a “maximum stroke length of 7.5 inches.” [129] No length of gauge, and the probe was as close as possible to, but not touching, the specimen. The probe was adjusted by increasing the probe until it touched the specimen. Then the probe was gradually reduced until it did not touch the specimen. Then the crosshead was set to zero. Considering the maximum travel distance, the distance would be approximately 0.10 inches. The crosshead speed was 10 inches/minute. The thickness was measured in the middle of the specimen. The film thickness , crosshead distance traveled, and peak load were used to determine perforation by the software. The drill rig was taken using a "KIM-WIPE" after each specimen. [130] Shrinkage Stress: Shrinkage stress was 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 strength of film samples was measured using a temperature rise test which was performed on an RSA-III Dynamic Mechanical analyzer (TA Instruments, New Castle, DE) with a film fastener. Film specimens "12.7 mm wide" and "63.5 mm long" were die cut from the film sample in either the machine direction (MD) or the transverse direction (CD) for testing. . Film thickness was measured by a Mitutoyo Absolute Digitizer (Model C112CEXB). This gauge had a maximum measuring range of 12.7 mm with a resolution of 0.001 mm. The average of three thickness measurements, at different locations on each film specimen, and the specimen width were used to calculate the cross-sectional film area (A), where "A = width x thickness" of the film that was used in shrink film tests. A standard TA Instruments film tension clamp was used for the measurement. The RSA-III oven was equilibrated at 25°C for at least 30 minutes before zeroing gap and axial force. The initial gap was adjusted to 20 mm. The film specimen was then attached at both the top and bottom. Typically, measurements for MD require only one-ply film. Since the shrinkage stress in the CD direction is normally low, two or four film layers are stacked together for each measurement to improve the signal-to-noise ratio. In such a case, the film thickness is the sum of all layers. In this work, a single layer was used in the MD direction and two layers were used in the CD direction. After the film reached the initial temperature of 25°C, the upper clamp was raised or lowered by hand slightly to obtain an axial force of -1.0 g. This was to ensure that no deformation or excessive stretching of the film occurred at the start of the test. Then the test was started. A constant fixation gap was maintained throughout the measurement. [131] The temperature ramp started 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 80°C to 160°C ramp, as the film shrank, the retraction force, measured by the force transducer, was recorded as a function of temperature for further analysis. The difference between the "peak force" and the "baseline value before the onset of peak shrink force" is considered the shrink force (F) of the film. Film shrinkage stress is the ratio of the shrinkage force (F) to the initial cross-sectional area (A) of the film. [132] For MD shrinkage stress, three film samples were tested, and an average reported. [133] For the CD shrinkage stress, three film samples were tested, and an average reported. EXPERIMENTAL First Ethylene-Based Polymers Example IE1 [134] The polymerization was carried out in a tubular reactor with three reaction zones. In each reaction zone, pressurized water was used for cooling and/or heating the reaction medium, circulating this water through the reactor jacket. The inlet pressure was 2100 bar, and the pressure drop across the entire tube reactor system was about 300 bar. Each reaction zone had an entrance and an exit. Each input stream consisted of the output stream from the previous reaction zone and/or an added ethylene-rich feed stream. Ethylene was supplied to a specification, which allowed for a trace amount (maximum of 5 moi ppm) of acetylene in the ethylene. The unconverted ethylene, and other gaseous components at the reactor outlet, were recycled through a low-pressure and a high-pressure recycling system, and were compressed and distributed through a booster system, a primary, and a hypercompressor ( secondary), according to the flow scheme shown in Figure 1. Organic peroxides were fed into each reaction zone (see Table 1). Acetone was used as a chain transfer agent, and was present at each reaction zone inlet originating from the low pressure and high pressure recycle streams (13 and 15), as well as from stream 7 and/or stream 6 mounted on newly injected CTA. The polymer was prepared at a melt index of 2.0 g/10 min. [135] After reaching the first peak temperature (maximum temperature) in reaction zone 1, the reaction medium was cooled with the help of pressurized water. At the exit of reaction zone 1, the reaction medium was then cooled by injecting a fresh, cold, ethylene-rich feed stream (20), and the reaction was restarted by feedback from an organic peroxide. This process was repeated at the end of the second reaction zone to allow for additional polymerization in the third reaction zone. The polymer was extruded and pelletized (about 30 pellets per gram) using a "single screw" extrusion system at a melting temperature of around 230-250°C. The weight ratio of the ethylene-rich feed streams (9:20:21) for the three reaction zones was 1.00:0.77:0.23. The values of R2 and R3 were each 2.22. R values are calculated in accordance with International Publication WO 2013/059042 (International Patent Application PCT/US 12/059469 filed October 10, 2012). Rn (n = number of reaction zone, n>1) is the ratio of "mass fraction of fresh ethylene fed to the first reaction zone (RZ1)" to "mass fraction of fresh ethylene fed to the in the reaction (RZn)" is (Rn = RZ1/RZn). The internal process speed was about 12.5, 9 and 11 m/s, respectively, for the first, second and third reaction zones. In this example of the invention, the weight ratio of the assembled CTA chains 7 and 6 was 1.1. Additional information can be found in Tables 2 and 3. Example 1E2 [136] Polymerization was carried out in a tubular reactor with three reaction zones, as discussed above, with the exception that both discharge streams (2 and 3) from the primary compressor were sent to the front feed stream of reactor 5. The weight ratio of ethylene rich feed streams (9:20:21) to the three reaction zones was 1.00:0.75:0 .25. The polymer was prepared at a melt index of 1.5 g/10 min. The values of R2 and R3 each approached the approached infinity (Do). In this example of the invention, the weight ratio of the assembled chains of CTA 7 and 6 was 0.09. Additional information can be found in Tables 2 and 3. CTA was propionaldehyde (PA). [137] In summary, to achieve tubular resins with high melt strength, suitable as a blending component in film compositions, typically in conjunction with a low or lower melt strength component, polymerization conditions need to be selected and balanced; for example, as discussed above. Important process parameters include maximum polymerization temperatures, reactor inlet pressure, conversion level, as well as the type, level and distribution of the chain transfer agent. Table 1: Initiators
    Table 2: Pressure and Temperature Conditions (first ethylene-based polymers)
    Table 3: Additional information (Ethylene-based first polymers)
    *When R2 and R3 are 2.16, the flow scheme in Figure 1 was used. In 1E2, both A and B primary (stream 2 and 3) were sent to stream 4. [138] Polymer properties are shown in Tables 4 and 5. Table 4: Polymer properties (LDPEs)

    *CE: Comparative Polymer; IE: First Ethylene-Based Polymer; AC: Autoclave based; Tub: Tubular. **Commercial polymers available from The Dow Chemical Company. s) "170°C data" are interpolated from 150°C and 190°C data. t): All MD metrics in this table obtained from GPC. Table 5: Polymer Properties (LDPEs)
    a) Mw(abs) < A x [(I2)B], where A=5.00 x 102 (kg/molee)/(dg/min)B, and B = -0.40 [Mw(abs) , GPC].b) MS C x where C = 13.5 cN/ (dg/min)', and D = -0.55 Melt Strength = MS, 190°C t): All MWD metrics in this table were obtained from GPC. [139] Table 6 contains the branches per 1000C as measured by I21C NMR. These LDPE polymers contain amyl, or C5 branches, which are not contained in substantially linear polyethylenes such as AFFINITY polyolefin plastomers, or Ziegler-Natta catalyzed LLDPE, such as DOWLEX polyethylene resins, both produced by The Dow Chemical Company. Each LDPE (IE1 and 1E2) shown in Table 6 contains more than or equal to 2.0 amyl groups (branches) per 1000 carbon atoms. Table 7 contains the results of unsaturation by IH NMR. Table 6: Branching Results in branches per 1000C by I3C NMR of the Inventive Examples and Comparative Examples
    ND = not detected. * The values in the C6+ column for the DOWLEX and AFFINITY samples represent C6 branches of octene only, and do not include chain ends. Table 7: Results by unsaturation by H NMR
    Formulations [140] Blown films were prepared, and physical properties measured, with different LDPEs and one LLDPE, LLDPE1 (DOWLEX 2045G). LLDPE1 had a melt index of 1.0 (MI or 12), and a density of 0.920 g/cm3. Films were prepared at 10% by weight, 20% by weight, and 80% by weight of the respective LDPE, based on the weight of LDPE and LLDPE1. [141] [147] Each formulation was combined in a MAGUIRE gravimetric mixer. A polymer processing aid (PPA), DYNAMAR FX-5920A, was added to each formulation. PPA was added to 1% by weight of the masterbatch, based on the total weight of the formulation. The PPA Master Lot (INGENIA AC-01-01, available from Ingenia Polymers) contained 8% by weight of DYNAMAR FX-5920A on a polyethylene backing. This equates to 800 ppm of PPA in the polymer. [142] LLDPE1 was also used as the LLDPE in films prepared at full production. The maximum yield was determined on samples prepared with 90% by weight of DOWLEX 2045G and 10% by weight of LDPE and 80% by weight of DOWLEX 2045G and 20% by weight of LDPE. Blown Film Production [143] Blown monolayer films were prepared in an "8 inch matrix" with a polyethylene "Davis II Standard Barrier screw". External cooling through an air ring and internal bubble cooling were used. General blown film parameters used to produce each blown film are shown in Table 8. The temperatures are the temperatures closest to the pellet feed hopper (Cylinder 1), and in ascending order as the polymer was extruded through the die. Films at normal rates were run at 250 lb/hr. Table 8: Blown Film Manufacturing Conditions for Films
    Film Production for Determination of Maximum Blown Film Production Rate [144] Film samples were prepared at a controlled speed and at a maximum rate. The controlled rate was 250 lb/h, which equates to a specific output rate of 10.0 lb/hr/inches for the die circumference. The die diameter used for the maximum production tests was an 8 inch die, so for the controlled rate, as an example, the conversion between the "lb/h" and "lb/h/inch" of the circumference of the matrix, is shown below. Likewise, such an equation can be used for other rates, such as the maximum rate, substituting the maximum rate in the equation below to determine the "lb/h/inch" of matrix circumference. Production Specifies = (250 Lb/h)/(8 inches * n) = 10 Lb/h/inch of die circumference. [145] The maximum production rate for a given sample was determined by increasing the production rate to the point where bubble stability was the limiting factor. The extrusion profile was maintained for both samples (standard rate and maximum rate), however, the melting temperature was higher for the maximum rate samples, due to the increase in shear speed, with higher engine speed (rpm , rotations per minute). Bubble stability, at maximum production rate, was determined by taking the bubble to the point where it would not settle in the air ring. At that point, the rate was reduced to where the bubble was reseated (maximum production rate) in the air ring, and then a sample was taken. The cooling in the bubble was adjusted by adjusting the air ring and maintaining the bubble. This process determined the maximum production rate while maintaining the stability of the bubble. [146] The film results are summarized in Tables 9-13. Table 9 shows the standard rate film results, with Film #1 being 100% LLDPE1, and Films #2-7 being 90% LLDPE1/10% LDPE. Film #2, containing 10% 1E2, shows advantages of low total and internal opacity, high puncture, high drying modulus, and high MD shrinkage stress. These properties are important for a variety of films with the desirable properties of good optical, mechanical properties, and shrinkage properties. This allows for the potential of LDPE for thinning, or thinning of the film, while maintaining good mechanical properties. [147] Table 10 shows the results of films at full rate, with Film #8 being 100% LLDPE1, and Films #9-14 being 90% LLDPE1/10% LDPE. This table shows a very important advantage of the 1E2, the improvement in blown film production when added even at low levels (10%) for LLDPE. At 10% LDPE, 1E2 has a higher blown film yield than any of the other LDPEs shown in Table 10, even those with much lower melt index (AGILITY 1001) and the wide molecular weight distribution autoclave resins such as as LDPE 6211. The % increase in maximum production during a given LDPE is shown in Table 10, which was calculated as: % Production Increase Due to 1E2 Compared to Reference LDPE = (Maximum Production Mix with 1E2 - Mixture of Maximum Production with Reference LDPE) X 100. Maximum Production Blend with Reference LDPE [148] These very substantial differences of 4-11% are new, and will translate into larger blown film lines until probably still differentiation and big gains in speed at which blown films can be produced, leading to reduced costs for the producer. Additionally, major film property advantages of good optics, puncture, modulus and shrinkage stress are maintained. [149] Table 11 contains the results for 20% LDPE added to LLDPE 1 for #15-20 Films, at 80% LLDPE1/20% LDPE, prepared at standard rate, and Table 12 contains the results for 20% LDPE added to LLDPE1 for 80% LLDPE1/20% LDPE Films, prepared at full rate. These results show generally good film properties, with particular emphasis on high shrinkage stress and high blown film production. The MD shrinkage stress of this grade is similar to that of much lower melt index resins (0.64) (AGILITY 1001), at standard rate, and higher than other blends with other LDPEs. At full production, the shrinkage stress results are even more differentiated, being much higher than any of the other films. The maximum yield in Table 12 is very new at the 20% LDPE level, being 11 - 19% higher than those observed for the other LDPEs, including lower melt index resins and autoclave resins. Such large production increases would be highly desirable for converters, allowing for much higher production rates. [150] Table 13 shows the results for films rich in 20% LLDPE1/80% LDPE LDPE #27-32 prepared at a standard rate. These results show good film properties together with very high shrinkage stress. Although maximum rates have not been executed for the 20% LLDPE1/80% LDPE films, based on the results at 10% LDPE and 20% LDPE, it is expected that 1E2 would also be of production advantage at this level of LDPE. [151] Figure 2 shows the maximum production a for the different LDPEs in LLDPE1 at 0%, 10%, and 20% LDPE, and the differentiation and advantage of 1E2 compared to all other LDPEs. Figure 3 shows the MD shrinkage stress for films prepared with maximum yield for the different LDPEs in LLDPE1 at 0%, 10%, and 20% LDPE, and the differentiation and advantage of 1E2 compared to all other LDPEs .









    权利要求:
    Claims (11)
    [0001]
    1. Composition containing low-density ethylene-based polymers, characterized in that it comprises the following: A) a first ethylene-based polymer, the first ethylene-based polymer being a low-density polyethylene (LDPE) formed by a high pressure free radical polymerization process and comprising the following properties: a) a Mw(abs) versus I2 ratio: Mw(abs) < A x [(I2)B], where A = 5.00 x 102 (kg/mole)/(dg/min)B, and B = -0.40, the MW(abs) being determined by gel permeation chromatography (GPC); and b) an MS (melting strength) ratio, measured at 190°C, versus I2: MS>Cx[(I2)D], where C = 13.5 cN/(dg/min)D and D = - 0, 55, and c) a melt index (I2) greater than 0.9 at 2.5 g/10 min, measured in accordance with ASTM D 1238, condition at 190°C/2.16 kg; and B) a second ethylene-based polymer, where the second ethylene-based polymer is a linear low density polyethylene (LLDPE); and the second ethylene-based polymer having a melt index (I2) from 0.1 to 4.0 g/10 min, measured in accordance with ASTM D 1238, condition at 190°C/2.16 kg.
    [0002]
    2. Composition according to claim 1, characterized in that the first ethylene-based polymer is present in an amount from "greater than zero" to 30 percent by weight, based on the sum of the weight of the first ethylene-based polymer and the second ethylene-based polymer.
    [0003]
    3. Composition according to claim 1, characterized in that the second ethylene-based polymer is an ethylene/α-olefin interpolymer.
    [0004]
    4. Composition according to claim 3, characterized in that the ethylene/α-olefin interpolymer is a heterogeneously branched ethylene/α-olefin interpolymer.
    [0005]
    5. Composition according to claim 1, characterized in that the first ethylene-based polymer has a melt strength (190°C) of 10 to 20 cN, measured according to ASTM D 1238, condition at 190° C/2.16 kg.
    [0006]
    6. Composition according to claim 1, characterized in that the first ethylene-based polymer has a G' (170°C) greater than or equal to 140 Pa, the rheology measurement to determine G' being performed in an environment of nitrogen, at 170°C and at a tension of 10%.
    [0007]
    7. Composition according to claim 1, characterized in that the first ethylene-based polymer has a density of 0.910-0.940 g/cm3 measured in accordance with ASTM D1920.
    [0008]
    8. Article, characterized in that it comprises one or more components formed from the composition defined in claim 1.
    [0009]
    9. Film, characterized in that it comprises one or more layers formed from the composition defined in claim 1.
    [0010]
    10. Film, according to claim 9, characterized in that the film comprises two or more layers.
    [0011]
    11. Film according to any one of claims 9 or 10, characterized in that the film has an MD shrinkage stress greater than 0.035 MPa (5.00 psi).
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    法律状态:
    2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-12-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-05-12| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2020-10-06| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-03-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-05-18| 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 21/05/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201361826263P| true| 2013-05-22|2013-05-22|
    US61/826,263|2013-05-22|
    PCT/US2014/038939|WO2014190036A1|2013-05-22|2014-05-21|Compositions containing low density ethylene-based polymers with high melt strength and films formed from the same|
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