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    PROCESS FOR FORMING AN ETHYLENE-BASED POLYMER COMPOSITION, POLYMER COMPOSITION AND FORMULATED COMPOSITION The invention provides a process for forming an ethylene-based polymer composition, the process comprising at least the following step 1: polymerize a first ethylene-based polymer in the presence of at least one molecular catalyst and a hydrocarbon chain transfer agent, and at a polymerization pressure of at least 14,000 psi; step 2: polymerize a second ethylene-based polymer.
    公开号:BR112013013634B1
    申请号:R112013013634-0
    申请日:2011-11-21
    公开日:2020-11-10
    发明作者:Sean W. Ewart；Sarat Munjal；Alfred E. Vigil；Teresa P. Karjala；Mehmet Demirors
    申请人:Dow Global Technologies Llc；
    IPC主号:
    专利说明:

    Background of the invention
    [0001] This invention relates to new polymer compositions based on ethylene in the presence of a molecular catalyst and a free radical initiator. In conventional polymerizations of ethylene-based polymers, catalysts, such as metallocene catalysts, post-metallocene catalysts and Ziegler-Natta catalysts, when used in a high pressure reactor, result in excessive fouling. In addition, such catalysts, under high pressure, are highly susceptible to decomposition, and form high molecular weight polymers and gels. These catalysts are also deactivated by polar impurities in the reactor. In a commercial production plant with an ethylene recycling system, polar impurities may be produced either from decomposition products of the free radical initiator or from agents used to deactivate the catalyst. Therefore, there is a need for polymerization processes to form new polymer compositions based on ethylene, which do not result in fouling of the reactor. There is an additional need for such processes that form smaller amounts of decomposition products and lower amounts of high molecular weight polymers and gels.
    [0002] GB 1205635 discloses the continuous polymerization of ethylene in two or more zones, which comprises passing ethylene through a first polymerization zone, at a pressure of not less than 1600 atmospheres and a temperature of not less than 125 ° C, at presence of a free radical initiator to form an ethylene polymer in at least one other reactor or a subsequent part of a multi-part reactor.
    [0003] International publication No. WO 2009/114661 discloses an ethylene polymer comprising amyl groups (about 0.1 to about 2.0 units per 1000 carbon atoms, and a peak melting temperature, Tm, in ° C , and a heat of fusion Hf, in J / g. The numerical values of Tm and Hf correspond to the relation Tm> (0.2143 * Hf) + 79.643.
    [0004] Additional polymerizations and / or polymers are disclosed in the following references: U.S. Patent Nos. 5084534, 5753578; international publication No. WO 2007/136494, WO 2011/032172; Rau et al., Kinetic Investigation of Metallocene-Catalyzed Polymerization of Ethylene at High Pressure, Chem. Eng. Technol. 25, 2002, 5, 494-498; Gdtz et al., Influence of Aluminum Alkyl Compounds on the High Pressure Polymerization of Ethylene with Ternary Metallocene-Based Catalysts. Investigation of Chain Transfer to Aluminum, Macromolecular Materials and Engineering 2002, 287, 16-22; Luft et al., And High Pressure Polymerization of Ethylene with a Homogeneous Metallocene Catalyst, Die Angewandte Makromolekulare Chemie, 212, 1993, 157-166.
    [0005] As discussed above, there remains a need for polymerization processes to form new polymer compositions based on ethylene, which do not result in scale in the reactor. There is also a need for such processes that do not result in obstructions. There is additionally a need for processes such as forming smaller amounts of decomposition products and smaller amounts of high molecular weight polymers and gels; and there is a need to form polymers with excellent processability. These needs were met by the following invention. Summary of the invention
    [0006] The invention provides a process for forming an ethylene-based polymer composition, the process comprising at least one of the following:
    [0007] Step 1: polymerize a first ethylene-based polymer in the presence of at least one molecular catalyst and a hydrocarbon transfer agent, and at a pressure of at least 96,526 kPa (14,000 psi);
    [0008] Step 2: polymerize a second polymer based on ethylene. Brief description of the drawings
    [0009] In the following, the invention will be better described in relation to the attached drawings, in which:
    [0010] Figures 1 to 4 represent a schematic example of reactor configuration of an inventive process. In figures 1 and 2, there may be more than two points of injection of catalyst in each step, and more than two points of injection of peroxide in each step;
    [0011] Figure 5 shows "DSC thermal flow vs. temperature" of examples 1-6;
    [0012] Figure 6 shows "DSC thermal flow vs. temperature" of examples 7-12;
    [0013] Figure 7 shows "Highest peak melting temperature vs. melting heat" by DSC of examples 1-12, and commercially available LDPE resins 1-30 and claim lines of WO 2009/114661;
    [0014] Figure 8 shows the TDGPC curve for examples 1-6;
    [0015] Figure 9 shows the TDGPC curve for examples 7-12;
    [0016] Figure 10 shows IR4 concentration detector scaled by CEF vs. temperature of examples 1-3;
    [0017] Figure 11 shows IR4 concentration detector scaled by CEF vs. temperature of examples 4-6;
    [0018] Figure 12 shows IRF concentration detector scaled by CEF vs. temperature of examples 7-9; and
    [0019] Figure 13 shows IRF concentration detector scaled by CEF vs. temperature of examples 10-12. Detailed description of the invention
    [0020] As discussed above, the invention provides a process for forming a polymer composition based on ethylene, the process comprising at least the following:
    [0021] Step 1: polymerize a first ethylene-based polymer in the presence of at least one molecular catalyst and a hydrocarbon chain transfer agent, and at a polymerization pressure of at least 96.526 kPa (14,000 psi);
    [0022] Step 2: polymerize a second polymer based on ethylene.
    [0023] An inventive process may comprise a combination of two or more embodiments as described here.
    [0024] In one embodiment, the second ethylene-based polymer is polymerized in the presence of a free radical initiator.
    [0025] In one embodiment, the first ethylene-based polymer and the second ethylene-based polymer are polymerized simultaneously.
    [0026] In one embodiment, the first ethylene-based polymer is polymerized first, and the second ethylene-based polymer is polymerized in the presence of the first ethylene-based polymer.
    [0027] In one embodiment, the polymerization pressure in step 1 is at least 124,105 kPa (18,000 psi).
    [0028] In one embodiment, the polymerization pressure in step 1 is at least 151,684 kPa (22,000 psi).
    [0029] In one embodiment, the polymerization pressure in step 1 is at least 179,263 (26,000 psi).
    [0030] In one embodiment, the polymerization pressure in step 1 is 137,895 kPa (20,000 psi) to 310,264 kPa (45,000 psi).
    [0031] In one embodiment, the polymerization pressure in step 1 is 172,368 kPa (25,000 psi) to 241,316 kPa (35,000 psi).
    [0032] In one embodiment, the polymerization pressure in step 1 and step 2 is 103,421 kPa (15,000 psi) to 413,685 kPa (60,000 psi), preferably from 137,895 kPa (20,000 psi) to 275790 kPa (40,000 psi).
    [0033] In one embodiment, the molecular catalyst is a zirconium complex of a polyvalent aryloxyether corresponding to the formula:
    where R20 independently at each occurrence is a divalent or inertively substituted aromatic linking group, each having 5 to 20 atoms not counting hydrogen;
    [0034] T3 is a valiant hydrocarbon or silane group, each having 1 to 20 atoms, not counting hydrogen, or an inertly substituted derivative thereof; and
    [0035] RD independently in each occurrence is a monovalent linker group having from 1 to 20 atoms, not counting hydrogen, or two RD groups together are a divalent linker group having 1 to 40 atoms, not counting hydrogen.
    [0036] In one embodiment, the molecular catalyst is soluble in supercritical ethylene.
    [0037] In one embodiment, the molecular catalyst is active at a polymerization temperature greater than, or equal to 200 ° C.
    [0038] In one embodiment, the molecular catalyst is active at a polymerization temperature greater than, or equal to 210 ° C.
    [0039] In one embodiment, the molecular catalyst is active at a polymerization temperature greater than, or equal to 220 ° C.
    [0040] In one embodiment, the molecular catalyst is selected from the group consisting of constricted geometry catalysts and post-metallocene catalysts (e.g., polyvalent aryloxyether compounds).
    [0041] In one embodiment, the molecular catalyst is selected from the group consisting of post-metallocene catalysts (e.g., polyvalent aryloxyether compounds). Some examples of post-metallocene are described in publication U.S, No. 2005/0164872 and international publication No. WO 2007/136494; each of which is incorporated by reference.
    [0042] In one embodiment, the molecular catalyst is selected from the group consisting of constrained geometry catalysts. Some examples of constrained geometry catalysts are described in U.S. Patent Nos. 5,272,236 and 5,278,272; each of which is incorporated by reference.
    [0043] In one embodiment, the catalyst has a very high chain transfer rate for ethylene.
    [0044] In one embodiment, the concentration of the catalyst in step 1 is 0.001 to 2 molar ppm, preferably 0.001 to 0.1 molar ppm, based on the total amount of ethylene added to the polymerization process.
    [0045] The molecular catalyst may comprise a combination of two or more embodiments as described here.
    [0046] In one embodiment, the first ethylene-based polymer is polymerized in the presence of an alumoxane cocatalyst. In a further embodiment, the alumoxane cocatalyst will be present in an amount of less than 50 molar ppm, preferably less than 40 molar ppm, and more preferably less than 30 molar ppm, based on the total amount of ethylene added to the polymerization process.
    [0047] In one embodiment, the hydrocarbon chain transfer agent of step 1 comprises from three to five carbon atoms.
    [0048] In one embodiment, the hydrocarbon chain transfer agent from step 1 In one embodiment, the hydrocarbon chain transfer agent from step 1 is a non-aromatic compound.
    [0049] In one embodiment, the hydrocarbon chain transfer agent of step 1 is selected from the groups consisting of C3-C5 aliphatic alkanes, and C3-C5 aliphatic alkynes.
    [0050] In one embodiment, the hydrocarbon chain transfer agent from step 1 is added to the reactor in an amount greater than, or equal to, 0.2 mole percent, based on the amount of ethylene added to this reactor.
    [0051] In one embodiment, the hydrocarbon chain transfer agent from step 1 is added to the reactor in an amount greater than, or equal to, 0.5 mole percent, based on the amount of ethylene added to this reactor.
    [0052] In one embodiment, the hydrocarbon chain transfer agent from step 1 is added to the reactor in an amount greater than, or equal to, 1 mol percent, based on the amount of ethylene added to this reactor.
    [0053] In one embodiment, the hydrocarbon chain transfer agent from step 1 is added to the reactor in an amount of less than, or equal to, 4 mole percent, based on the amount of ethylene added to this reactor.
    [0054] In one embodiment, the hydrocarbon chain transfer agent from step 1 is added to the reactor in an amount of less than, or equal to, 3.5 mole percent, based on the amount of ethylene added to this reactor .
    [0055] In one embodiment, the hydrocarbon chain transfer agent from step 1 is added to the reactor in an amount of less than, or equal to, 3 mole percent, based on the amount of ethylene added to this reactor.
    [0056] In one embodiment, the hydrocarbon chain transfer agent from step 1 is added to the reactor in an amount of 1 to 3.5 mole percent, based on the amount of ethylene added to this reactor.
    [0057] In one embodiment, the hydrocarbon chain transfer agent from step 1 is added to the reactor in an amount of 2 to 3 mole percent, based on the amount of ethylene added to this reactor.
    [0058] In one embodiment, the hydrocarbon chain transfer agent will be present in step 1 from 0.5 to 10 moles%, preferably from 0.5 to 5 moles%, based on the amount of ethylene added to this reactor.
    [0059] The hydrocarbon chain transfer agent may comprise a combination of two or more embodiments as described here.
    [0060] In one embodiment, the free radical initiator is a peroxide. Some examples of peroxides include, but are not limited to, cyclic peroxides, diacyl peroxides, dialkyl peroxides, hydroperoxides, peroxycarbonates, peroxydicarbonates, peroxyesters, and peroxyacetals.
    [0061] In one embodiment, the free radical initiator is a peroxide that produces a minimal amount of, and preferably none, polar "cage" product, and preferably does not produce carbon dioxide as a "Cage" product. Polar "Cage" products are described in M. Buback et al., Initiator Efficiency of ter — Alkyl Peroxyesters in High-Pressure Ethene Polymerization, Macromol. Chem. Phys., 2007, 208, 772-783, incorporated herein by reference. Examples of such peroxides include 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane; 1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane; and di-tert-butyl peroxide.
    [0062] In one embodiment, the polymerization temperature in step 1 is greater than, or equal to, 195 ° C.
    [0063] In one embodiment, the polymerization temperature in step 1 is greater than, or equal to, 200 ° C.
    [0064] In one embodiment, the polymerization temperature in step 1 is greater than, or equal to, 210 ° C.
    [0065] In one embodiment, the polymerization temperature in step 1 is greater than, or equal to, 220 ° C.
    [0066] In one embodiment, the polymerization temperature in step 1 is 195 ° C to 260 ° C.
    [0067] In one embodiment, the polymerization temperature in step 1 is 200 ° C to 240 ° C.
    [0068] In one embodiment, the polymerization temperature in step 1 is 210 ° C to 230 ° C.
    [0069] In one embodiment, the polymerization temperature in step 2 is 180 ° C to 310 ° C.
    [0070] In one embodiment, the polymerization temperature in step 2 is 200 ° C to 280 ° C.
    [0071] In one embodiment, no hydrogen is added in step 1.
    [0072] In one embodiment, no hydrogen is added in step 2.
    [0073] In one embodiment, no hydrogen is added in step 1 or step 2.
    [0074] In one embodiment, the process does not comprise a compound containing boron.
    [0075] In one embodiment, the process additionally comprises polymerizing a third polymer based on ethylene.
    [0076] In one embodiment, at least one alkyl aluminum is added to the process after step 2.
    [0077] An alkyl aluminum is a compound with at least one aluminum attached to one or more alkyl groups, such as triethyl aluminum or triisobutyl aluminum. These also include aluminoxane-like species such as MAO or MMAO-3A (CAS # 146905-79-5).
    [0078] In one embodiment, at least one polyalkylene glycol is added to the process after step 2. In an additional embodiment, the polyalkylene glycol has a numerical average molecular weight of at least 200 g / mol, or at least 250 g / mol , or at least 300 g / mol.
    [0079] In one embodiment, polyalkylene glycol is a compound of the formula HO (CH2CHRO) nH, where R is an alkyl or hydrogen group. Preferably, R = H (polyethylene glycol). Preferably, n is 3 to 10 repetitive units.
    [0080] In one embodiment, polar impurities are removed in the ethylene recycling stream by excess aluminum alkyl or by molecular sieve beds in the ethylene recycling stream.
    [0081] In one embodiment, a non-volatile catalyst poison is used to deactivate the catalyst before it leaves the final reactor in the polymerization process.
    [0082] In one embodiment, the polymerization process is a continuous process.
    [0083] In one embodiment, the first ethylene-based polymer is a polyethylene homopolymer.
    [0084] In one embodiment, the second ethylene-based polymer is a polyethylene homopolymer.
    [0085] In one embodiment, the first ethylene-based polymer is a polyethylene homopolymer and the second ethylene-based polymer is a polyethylene homopolymer.
    [0086] In one embodiment, the ethylene-based polymer composition has a percentage crystallinity of at least 45 percent, as determined by DSC.
    [0087] In one embodiment, the ethylene-based polymer composition has a percentage crystallinity of at least 50 percent, as determined by DSC.
    [0088] In one embodiment, the ethylene-based polymer composition has at least a melting point greater than 115 ° C, as determined by DSC.
    [0089] In one embodiment, the ethylene-based polymer composition has at least a melting point greater than 120 ° C, as determined by DSC.
    [0090] In one embodiment, the inventive process takes place in at least one autoclave reactor.
    [0091] In one embodiment, the inventive process takes place in at least one tubular reactor.
    [0092] In one embodiment, the inventive process takes place in at least one autoclave reactor and in at least one tubular reactor. In a further embodiment, the at least one autoclave reactor and the at least one tubular reactor are connected in series.
    [0093] An inventive process may comprise a combination of two or more embodiments as described here.
    [0094] The invention also provides a polymer composition formed by the inventive process.
    [0095] In one embodiment, the polymer composition has a fraction per CEF, at a temperature of at least 85 ° C, of at least 5 weight percent (based on the weight of the polymer composition), and which has a trefBr value greater than 0.5.
    [0096] In one embodiment, the ethylene-based polymer composition has at least a melting point greater than 115 ° C, as determined by DSC.
    [0097] In one embodiment, the ethylene-based polymer composition has at least a melting point greater than 120 ° C, as determined by DSC.
    [0098] In one embodiment, the ethylene-based polymer composition has a density greater than, or equal to, 0.90 g / cm3, preferably greater than, or equal to 0.91 g / cm3, more preferably greater than, or equal to 0.92 g / cm3. (1 cm3 = 1 cc).
    [0099] In one embodiment, the ethylene-based polymer composition has a density less than, or equal to, 0.940 g / cm3, or less than, or equal to 0.935 g / cm3. (1 cm3 = 1 cc).
    [0100] In one embodiment, the ethylene-based polymer composition has a melt index (I2) less than, or equal to, 100 dg / min., Preferably less than, or equal to, 50 dg / min., More preferably less than, or equal to, 20 dg / min.
    [0101] An inventive composition may comprise a combination of two or more embodiments as described here.
    [0102] The invention also provides a composition comprising an inventive polymer composition and at least one additive.
    [0103] An inventive composition may comprise a combination of two or more embodiments as described here.
    [0104] The invention also provides an article comprising at least one component formed from the inventive polymer composition or an inventive composition.
    [0105] Polymerization
    [0106] It has been found that using a catalyst that has a very high transfer rate for ethylene, the effect of ethylene concentration on the molecular weight of the polymer can be eliminated. It was also discovered that these catalysts admit an increased pressure and an increased ethylene concentration, which, in turn, increases both the rate of propagation and the rate of chain transfer, keeping the molecular weight of the polymer almost constant with increasing pressure.
    [0107] Hydrogen in a high pressure reactor has been shown to cause increased secondary conversions, increased decomposition, increased hydrogenation by-products and increased metal brittleness. It has been found that using a catalyst that transfers chains to ethylene, and that has a strong temperature response to the chain transfer rate, the reactor temperature can be used as a molecular weight control, and hydrogen can be eliminated from the reactor.
    [0108] Boron activators, such as trityl borate, have been shown to decompose into free radicals, and cause decomposition at high temperatures and ethylene pressures. It has been found that by choosing a catalyst that can be activated with just one alumoxane cocatalyst, these decomposition-sensitive catalysts can be eliminated from the system.
    [0109] The fouling in high pressure reactors may occur due to the previous low molecular weight LDPE, started thermally or by eventual oxygen in the system. It has been discovered that a hydrocarbon chain transfer agent can be used in a way to reduce the molecular weight and reduce the fouling tendencies of this previous LDPE. CTAs that do not join the main chain may be preferred in some cases, and the density of high densities will remain high. Incorporating CTA's such as propylene, butene, hydroxide, and octene may be preferred in other applications, in order to lower the density of the base linear polyethylene, and give different characteristics of physical properties to the polyethylene, due to the lower density, as well as the length of the side chain resulting from the CTA / monomer.
    [0110] In a commercial process, typically all polar compounds produced in the reactor will recirculate and disable a molecular weight. These polar compounds may include peroxide decomposition products used to constitute the LDPE portion of the polymer composition or catalyst poison added after the first reactor to prevent further polymerization. For the initiated processes described here, it has been found that these impurities can be purged by adding an excess of aluminum alkyl to the reactor, or they can be avoided using a carbon-based free radical initiator or a non-volatile catalyst poison, such as polyethylene glycol, BHT or glycerol. Optionally, molecular sieve beds can be added to the ethylene recycling line to remove any polar impurities before it is recycled back to the reactor.
    [0111] In one embodiment, in a two-reactor process, the catalyst poison is added after the second reactor, and the alkyl aluminum purger is added either to the first reactor, or to the incoming ethylene stream before the first reactor. In this way, the impurity purge will take place in the second reactor, and the ethylene recycling stream must remain clean.
    [0112] In one embodiment, the alkyl aluminum purger is added after the second, but before the catalyst poison.
    [0113] Examples of some reactor configurations for the inventive process are shown in figures 1 and 2. The inventive process can be operated in one or more tubular reactors, or autoclave / tubular configurations. In one embodiment, the partition between the first ethylene-based polymer and the second ethylene-based polymer is controlled in the tubular process using different tube lengths for each reaction zone. In another embodiment, in an autoclave / tubular process or autoclave process, the partition is controlled by dividing the autoclave into separate zones with deflectors. Each zone can be used to produce either the first ethylene-based polymer or the second ethylene-based polymer.
    [0114] The ethylene used in the production of ethylene-based polymers may be purified ethylene, which is obtained by removing polar components from the loop recycling chain and fresh ethylene.
    [0115] In one embodiment, the first ethylene-based polymer is a polyethylene homopolymer.
    [0116] In another embodiment, the first ethylene-based polymer comprises ethylene and one or more comonomers, and preferably a comonomer. Comonomers include, but are not limited to, α-olefin comonomers, typically α-olefins having no more than 20 carbon atoms. For example, a-olefin comonomers may have 3 to 10 carbon atoms; or, alternatively, a-olefin comonomers may have 3 to 8 carbon atoms. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1 - pentene.
    [0117] In one embodiment, the second ethylene-based polymer is a polyethylene homopolymer.
    [0118] In another embodiment, the second ethylene-based polymer comprises ethylene and one or more comonomers, and preferably a comonomer. Comonomers that may be used to form highly branched ethylene-based polymers include, but are not limited to, α-olefin comonomers, typically α-olefins having no more than 20 carbon atoms. For example, a-olefin comonomers may have 3 to 10 carbon atoms; or, alternatively, a-olefin comonomers may have 3 to 8 carbon atoms. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1 -penny. In the alternative, exemplary comonomers include, but are not limited to, C3-C8 α, β-unsaturated carboxylic acids, in particular maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid, and crotonic acid derived from C3- carboxylic acids C8 α, β-unsaturated, for example, esters of C3-C15 carboxylic acids, in particular esters of C1-C6 alkanols, or anhydrides, in particular methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, tertiary methacrylate butyl, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, tert-butyl acrylate, methacrylic anhydride, maleic anhydride, and itaconic anhydride. In another alternative, exemplary comonomers include, but are not limited to, vinyl carboxylates, for example, vinyl acetate. In another alternative, exemplary comonomers include, but are not limited to, n-butyl acrylate, acrylic acid and methacrylic acid. In an additional embodiment, the comonomer (s) is (are) added to the polymerization in an amount less than 5 moles%, or less than 2 moles%, based on the amount of ethylene added to the polymerization process . Additions
    [0119] A polymer composition based on ethylene may comprise at least one additive. Additives include, but are not limited to, stabilizers, plasticizers, and fillers. Stabilizers include, for example, antioxidants, such as IRGANOX 1010 and IRGAFOS 168 (Ciba Specialty Chemicals, Glattbrugg, Switzerland). In general, polymers are treated with one or more stabilizers before extrusion or other melt processes. In processes of other embodiments, other polymeric additives include, but are not limited to, ultraviolet light absorbers, antistatic agents, pigments, dyes, nucleating agents, fillers, glidants, flame retardants, plasticizers, processing aids, lubricants, stabilizers, smoke inhibitors, viscosity controlling agents, and anti-blocking agents. The ethylene-based polymer composition may, for example, comprise less than 10 percent by weight combined of one or more additives, based on the weight of the final composition.
    [0120] Plasticizers include, but are not limited to, phthalates, such as dioctyl phthalate and diisobutyl phthalate, natural oils such as lanolin and paraffin, naphthenic and aromatic oils obtained from petroleum refining, and liquid resins from raw materials from pitch or oil. Exemplary classes of oils useful as processing aids include white mineral oil such as KAYDOL oil (Chemtura Corp., Middlebury, Conn.) And SHELLFLEX 371 naphthenic oil (Shell Lubricants, Houston, Tex.). Another suitable oil is TUFLO oil (Lyondell Lubricants; Houston, Tex.).
    [0121] Loads include, but are not limited to, organic or inorganic particles, including clays, talc, titanium dioxide, zeolites, powdered metals, organic and inorganic fillers, including carbon fibers, silicon nitride fibers, wire or weft of steel, and nylon or polyester threads, nanodimensioned particles, clays.
    [0122] Ethylene-based compositions may be mixed or mixed with other polymers, such as other olefin-based polymers. Polymers include, for example, thermoplastic and non-thermoplastic polymers, including natural or synthetic polymers. Exemplary mixing polymers include polypropylene (both impact modifier polypropylene, isotactic polypropylene, atactic polypropylene, and random ethylene / propylene copolymers, various types of polyethylene, including high pressure, free radical LDPE, Ziegler-Natta LLDPE, PE metallocene, including multiple reactor PE (mixtures "intra-reactors of Ziegler-Natta PE, metallocene PE, such as products disclosed in US Patent No. 6,545,088 (Kolthammer, et al.); 6,538,070 (Cardwell et al.); 6,566,446 (Parikh et al.); 5,844,045 (Kolthammer et al); 5,869,575 (Kolthammer et al.); and 6,448,341 (Kolthammer et al.), ethylene vinyl acetate (EVA), ethylene / vinyl alcohol block copolymers, polystyrene, impact-modified polystyrene, ABS, styrene / butadiene block copolymers and hydrogenated derivatives of these SBS and SEBS), and thermoplastic polyurethanes Homogeneous polymers such as olefin plastomers, bas copolymers also based on ethylene and propylene (for example, commercially available polymers under the trade name Plastomers and Elastomers VERSIFYMR (The Dow Chemical Company), SURPASS (Nova Chemicals), and VISTAMAXX (ExxonMobil Chemical Co.)) may also be used. applications
    [0123] Ethylene-based polymer compositions may be employed in a variety of conventional thermoplastic fabrication processes to produce useful articles, including objects comprising at least one film layer, such as a monolayer film, or at least one layer in a multilayer film prepared by casting, blowing, calendering, or extrusion coating processes; molded articles, such as blow-molded, injection-molded, or rotational molded articles; extrusions; fibers; and woven or non-woven cloths. Definitions
    [0124] The term "composition", as used here, includes a mixture of materials comprising the composition, as well as reaction products and decomposition products formed from materials of the composition.
    [0125] The term "ethylene-based polymer composition", as used herein, refers to a composition that comprises at least one ethylene-based polymer, and typically comprises at least two ethylene-based polymers. These compositions may also include a first polymer based on unreacted ethylene, as described here, and / or a polymer based on ethylene polymerized via free radical (e.g. LDPE).
    [0126] The second ethylene-based polymer, as described here, is formed from at least the following: a) the first ethylene-based polymer, as described here, and b) ethylene. In a preferred embodiment, the amount of ethylene is greater than 60 weight percent, preferably greater than 80 weight percent ethylene, based on the added weight of the first ethylene and ethylene based polymer.
    [0127] The term "polymer", as used here, refers to a polymeric compound prepared by polymerizing monomers, of the same or different types. The generic term polymer, therefore, encompasses the term homopolymer (used to refer to polymers prepared from a single type of monomer, with the understanding that trace amounts of impurities may be incorporated into the structure of the polymer), and the term interpolymer as defined below.
    [0128] The term "interpolymer" means a polymer prepared by the polymerization of at least two different types of monomers. The generic term interpolymer includes copolymers (generally used to refer to polymers prepared from two different types of monomers) and polymers prepared from more than two different types of monomers.
    [0129] The term "olefin-based polymer", as used here, refers to a polymer comprising, in the polymerized form, a major amount of olefin monomer, for example, ethylene or propylene (based on the weight of the polymer ), and optionally can comprise one or more comonomers.
    [0130] The term "ethylene-based polymer", as used here, refers to a polymer that comprises, in polymerized form, a majority amount of ethylene monomer (based on the weight of the polymer), and may optionally comprise a or more comonomers.
    [0131] The term "ethylene / a-olefin interpolymer", as used here, refers to a copolymer that comprises, in polymerized form, a major amount of ethylene (based on the weight of the copolymer), and an a- olefin, as the only two types of monomers.
    [0132] The term "hydrocarbon", as used here, refers to a chemical compound that comprises only hydrogen and carbon atoms.
    [0133] The term "molecular catalyst", as used here, refers to a catalyst that can be defined by a molecular structure. The term does not include Ziegler-Natta catalysts, which can be defined by more than one molecular structure.
    [0134] The term "boron-containing compound", as used herein, refers to a chemical compound that contains at least one boron atom.
    [0135] The term "comprising", "including", "having", and derivatives thereof, are not intended to exclude the presence of any additional component, step or procedure, whether or not it is disclosed herein. In order to avoid any doubt, all compositions claimed here by the use of the term "comprising" may include any additive, adjuvant, or compound, polymeric or not, additional, unless expressly noted to the contrary. In contrast, the term "essentially consisting of" excludes any other component, step or procedure from the scope of any subsequent observation, except those not essential to operability. The term "consisting of" excludes any component, step or procedure not specifically outlined or listed. Test Methods
    [0136] Unless otherwise noted, all test methods are current at the time of filing of provisional U.S. Patent Application No. 61 / 419,560. Density
    [0137] Density was measured according to ASTM D792, Method B. The polymer is heated to 374 ° F and pressed to a pressure of 2000 lbs force (pneumatic press manufactured by Tetrahedron Associates Inc.). The sample is then cooled to 75 ° F, while maintaining a pressure of 2000 1b under pressure to form a "5" x 1.25 "x 1.8" polymer plate. Three samples with the following dimensions "1.25 in. X 5 in. X 1/8 in." were cut using a Gotech Press. These samples were used to measure density based on the Archimedes principle in a controlled isopropyl alcohol bath at 23 ° C. Fusion index
    [0138] The melting index, or I2, is measured according to ASTM D 1238, condition 190 ° C / 2.16 kg, and is reported as grams eluted for 10 minutes. I10 is measured according to ASTM D 1238, condition 190 ° C / 10 kg, and is reported as grams eluted for 10 minutes. Differential Scanning Calorimetry
    [0139] Differential Scanning Calorimetry (DSC) can be used to measure the melting and crystallization behavior of a polymer over a wide temperature range. For example, a TA Instruments DS1000 QC with an RCS (refrigerated cooling system) and a self-sampler are used to perform this analysis. During the test, a nitrogen purge flow of 50 mL / min is used. Each sample is melted into a thin film at about 175 ° C; the molten sample is then cooled in air to room temperature (~ 25 ° C). A 3- 10 mg test body, "6 mm diameter" is extracted from the cooled, weighed polymer placed in a light aluminum pan (about 50 mg) and closed by seaming. The analysis is then performed to determine the thermal properties.
    [0140] The thermal behavior of the sample is determined by ramping the sample temperature up and down to create a thermal flow profile against temperature. First, the sample is heated quickly to 180 ° C, and maintained isothermally for 3 minutes, in order to remove its thermal history. The sample is then cooled to -40 ° C, at a cooling rate of 10 ° C / min and maintained at -40 ° C for 3 minutes. The sample is then heated to 150 ° C at a heating rate of 10 ° C / min. The cooling and second heating curves are recorded. The heating curve is analyzed by adjusting the extreme baseline points from the start of crystallization to -20 ° C. The heating curve is analyzed by adjusting the extreme points of the baseline from -20 ° C until the end of the melt. The values determined are peak melting temperature (Tm), peak crystallization temperature (Tc), heat of melting (Hf) (in Joules per gram), and the% crystallinity calculated for polyethylene samples using equation 1: Crystallinity% = ((Hf) / (292 J / g)) X 100 (Eq. 1)
    [0141] The melting heat (Hf) and the peak melting temperature are reported from the second curve. The peak crystallization temperature is determined from the cooling curve. Gel Permeation Chromatography (GPC)
    [0142] The GPC system consists of a 150 ° C Waters high temperature chromatograph (Millford, MA) (other suitable high temperature GPC instruments include Model 210 and Model 220 from Polymer Laboratories, (Shropshire, UK)) , equipped with an onboard differential refractometer (IR). Additional detectors may include a Polymer ChAR IR4 infrared detector (Valencia, Spain), Precision Detectors Model 1040 binary laser light scattering detector (Amhetst, MA), and a Viscotek 150R 4 capillary solution viscometer (Houston , TX). A GPC with at least two independent detectors and at least one of the first detectors is sometimes referred to as "GPC-3D", while the term "GPC" only generally refers to a conventional GPC. Depending on the sample, a 15-degree or 90-degree angle light scatter is used for calculation purposes.
    [0143] Data collection is performed using Viscotek TriSEC, Version 3 software, and a 4-channel Viscotek Data Manager DM400. The system is also equipped with an in-line solvent degassing device from Polymer Laboratories (Shropshire, UK). Suitable high temperature GPC columns can be used, such as four 13 micron "Shodex HT803 13" 30 cm long "columns or four 30 cm long columns with 20 micron mixed pore size fill from Polymer Labs (MixA LS, Polymer Labs) The sample carousel compartment is operated at 150 ° C. The samples are prepared at a concentration of "0.1 gram of polymer" in 50 milliliters of solvent. The chromatographic solvent and the sample preparation contains 200 ppm of butylated hydroxy toluene (BHT). Both solvents are sparged with nitrogen. The polyethylene samples are gently stirred at 160 ° C for four hours. The injection volume is 200 microliters. through the GPC is adjusted to 1 mL / minute.
    [0144] The GPC column set is calibrated before processing the examples by passing twenty-one polystyrene standards of narrow molecular weight distribution. The molecular weight (MW) of the standards ranges from 580 to 8,400,000, and the standards are contained in 6 mixtures of "cocktails". Each mixture of standards has at least a decade of separation between individual molecular weights. Standard mixtures are purchased from Polymer Laboratories (Shropshire, UK). Polystyrene standards are prepared with "0.025 grams" in 50 milliliters of solvent for molecular weights equal to or greater than 1,000,000 grams / mol, and with "0.05 g" in 50 mL of solvent for molecular weights less than 1,000 .000 grams / mol. The polystyrene standards are dissolved at 80 ° C with gentle agitation for 30 minutes. Mixtures with narrow standards are processed first and in order to reduce the component with the highest molecular weight to minimize degradation. The peak molecular weights of the polystyrene standards are converted to Mw of polyethylene using the Mark-Houwink K and a values (sometimes referred to as a) mentioned below for polystyrene and polyethylene. See the example section for a demonstration of this procedure.
    [0145] With GPC-3D the absolute weight average molecular weight (("Mw abS") and the intrinsic viscosity are also obtained independently from narrow polyethylene standards using the same conditions mentioned above. These narrow polyethylene standards can be obtained from Polymer Laboratories (Shropshire, United Kingdom; parts PL2650-0101 and PL2350-0102).
    [0146] The systematic approach for determining multi-detector lag is performed in a manner consistent with that published by Balke, Mourey et al. (Mourey and Balke, Chromatography Polym., Chapter 12, (1992)) (Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym., Chapter 13, (1992)), optimizing the log results (Mw and intrinsic viscosity) of the triple detector results from the wide polystyrene Dow 1683 (American Polymer Standards Corp., Mentor, OH) or its equivalent to the results of narrow column calibration from the narrow polystyrene standards 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 (1987)) The overall injected concentration used in determining the molecular weight is obtained from the mass detector area, and the constant mass detector constant derived from a suitable linear polyethylene homopolymer, or one of the polyethylene standards of known weight average molecular weight The calculated molecular weights are obtained using a light scattering constant, derived from one or more of the polyethylene standards mentioned below and a refractive index concentration coefficient, dn / dc, of 0.104. 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. was performed using the methods described by the manufacturer, or alternatively using the published values of suitable linear standards such as Standard Reference Materials (SRM) 1475a, 1482a, 1483, or 1484a. Chromatographic concentrations are assumed to be low enough to eliminate the application of 2nd viral coefficient effects (concentration or molecular weight effects). g 'by GPC-3D
    [0147] The index (g ') for the sample polymer is determined first by calibrating the light scattering, viscosity, and concentration detectors, described in the Gel Permeation Chromatography method above, with SRM 1475a polyethylene homopolymer (or an equivalent reference). The light scattering and viscometer lags are determined relative to the concentration detector, as described in the calibration. The baselines are subtracted from the light scattering, viscometer, and concentration chromatograms that indicate the presence of polymer detectable from the refractive index chromatogram. A linear homopolymer polyethylene is used to establish a linear Mark-Houwink (MH) reference line by injecting a wide molecular weight polyethylene reference, such as a 1475a standard, calculating the data file and recording the intrinsic (IV) viscosity and the molecular weight (Mw), each derived from the light scattering and viscosity detectors, respectively, and the concentration, as determined by the IR detector mass constant for each chromatographic slice. For sample analysis, the procedure for each chromatographic slice is repeated in order to obtain a Mark-Houwink line. Note that for some samples the lower molecular weights, the intrinsic viscosity and the molecular weight data may need to be extrapolated, in such a way that the measured molecular weight and viscosity approximate asymptotically a GPC calibration curve of linear homopolymer. To this end, many highly branched ethylene-based polymer samples require that the linear reference line be shifted slightly to count for the contribution of the short chain branch before proceeding with the calculation of the long chain branch index (g ') .
    [0148] An original of g ("g-prime") (g ± ') is calculated for each chromatographic slice of the branched sample (i) and measuring the molecular weight Mi) according to equation 2 "gi (IV sample) / Linear IV reference) (Eq. 2) where the calculation uses IV reference, with equivalent molecular weight, Mj, in the reference sample, in other words, the IV slice sample (i) and the reference IV slice (j ) have the same molecular weight (Mi = Mj). For simplicity, IVnθfθ linear linear slices are calculated from a fifth order polynomial fit adjusted for the Mark-Houwink plot. The ratio of IV, or g /, is only obtained with molecular weights higher than 3,500 due to the signal-to-noise limitations in the light scattering data.The number of branches for each slice (i) can be assumed by assuming an epsilon viscosity factor of 0.75:

    [0149] Finally, the average LCBf quantity per 1000
    carbons in the polymer across all slices (i) can be determined using equation 4: (Eq. 4) gpcBR Branch Index by GPC-3D
    [0150] In the GPC-3D configuration, the polyethylene and polystyrene standards can be used to measure Mark-Houwink, K and a constants, independently for each of the two types of polymer, polystyrene and polyethylene. These may be useful for refining Williams and Ward's equivalent molecular weights of polyethylene in the application of the following methods.
    [0151] 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. Integration windows are then adjusted to ensure integration of the entire low molecular weight retention volume rate into the light scattering and viscometer chromatograms that indicate the presence of detectable polymer in the refractive index chromatogram. Linear polyethylene standards are then used to establish Mark-Houwink constants for polyethylene and polystyrene as previously described. Once the constants are obtained, the two values are then used to construct conventional linear reference ("cc") calibrations for polyethylene molecular weight and intrinsic polyethylene viscosity as a function of the elution volume, as shown in equations 5 and 6:


    [0152] The gpcBR branch index is a robust method for characterizing long chain branches. See Yau, Wallace W., “Examples of Using 3D-GPC - TREF for Polyolefin Characterization”, Macromol. Symp., 2007, 257, 29- 45. The index avoids the GPC-3D slice-by-slice calculations traditionally used for determining g 'values in favor of entire polymer detector areas and branch and product frequency calculations punctual area. For GPC-3D data, the sample's Mw mass can be obtained by the light scattering (LS) detector using the peak area method. The method avoids the slice-to-slice ratio of the light detector to the concentration detector signal as required in the determination of g '.

    [0153] The area calculation in equation 7 offers more precision since a global sample area is much less sensitive to variation caused by detector noise and baseline GPC adjustments and integration limits. Most importantly, the peak area calculation is not affected by the volume detector lags. Similarly, the intrinsic (IV) viscosity of a high-precision sample is obtained by the area method shown in equation 8:
    where DPi means the differential pressure signal monitored directly from the inline viscometer.
    [0154] To determine the gpcBR branching index, the area of light diffusion elution 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 (IV) or [η]) of the sample.
    [0155] Initially, the molecular weight and the intrinsic viscosity for the standard linear polyethylene sample, such as SRM 1475a or an equivalent, are determined using conventional calibrations for both the molecular weight and the intrinsic viscosity as a function of the elution volume. , according to equations 9 and 10:

    [0156] Equation 11 is used to determine the gpcBR branching index:
    where {η] is the intrinsic viscosity, {η] c <is the intrinsic viscosity from the conventional calibration, Mw is the weighted average molecular weight and Mwcx is the weighted average molecular weight of the conventional calibration. 0 Mw by light scattering (LS) using equation (7) is commonly referred to as the absolute Mw, while Mw, cc of equation 9 using the conventional GPC molecular weight calibration curve is often referred to as the polymer chain Mw . All statistical values with the subscript "cc" are determined using their respective elution volumes, the corresponding conventional calibration as previously described, and the concentration (Ci) derived from the mass detector response. Unsubscribed values are measured values based on the response of the mass detector. Unsubscribed Values are measured values based on the mass detector, LALLS, and viscometer areas. The KPE value is iteratively adjusted until the linear reference sample has a measured gpcBR value of zero. For example, the final values for ae 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.
    [0157] Once the K and a values have been determined, the procedure is repeated using the branched samples. Branched samples are analyzed using the final Mark-Houwink constants as the best "cc" calibration values and applying equations 7-11.
    [0158] The interpretation of gpcBR is straightforward. For linear polymers, the gpcBR calculated by equation 11 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 higher than zero, especially with high levels of LCB since the measured polymer's Mw will be higher than the MWfCC, and the IVCC will be higher than the measured polymer's IV. In fact, the gpcBR value represents the fractional change of IV due to the effect of the contraction of the molecular size as a result of the polymer branching. A gpcBR value of 0.5 to 2.0 would mean a contraction effect of IV molecular size at the level of 50% and 200%, respectively, versus a linear polymer molecule of equivalent weight.
    [0159] For these particular examples, the advantage of using gpcBR compared to the g 'index and frequency calculations is due to the higher precision of gpcBR. All parameters used to determine the gpcBR index are obtained with good precision, and are not detrimentally affected by the low response of the GPC-3D detector to 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. In other particular cases, other methods for determining Mw moments may be preferable to the aforementioned technique. CEF method
    [0160] The polymer branch distribution analysis is performed by Crystallization Elution Fractionation (CEF) (PolymerChar in Spain) (B. Monrabal et al., Macromol. Symp 257, 71-79 (2007)). The CEF instrument is equipped with three detectors: an IR4 infrared detector to measure polymer concentration, and a bicapillary viscometer for both the Polymer ChAR (Valencia, Spain), and the Model 2040 biangular laser light scattering detector from Precision Detectors (Amherst, MA). Ortho-dichlorobenzene (ODCB) with 600 ppm of butylated hydroxytoluene antioxidant (BHT) is used as the solvent. Sample preparation is performed with a self-sampler at 160 ° C for 2 hours, under agitation at 4 mg / mL (unless otherwise specified). The injection volume is 300 pL. The upper oven temperature, where the detectors and injection loop are located, is 150 ° C. The temperature profile of the CEF is: crystallization at 3 ° C / min. 110 ° C to 30 ° C, thermal equilibrium at 30 ° C for 5 minutes, and elution at 30 ° C / min. from 30 ° C to 140 ° C. The flow rate during crystallization is 0.052 ml / min. The flow rate during elution is 0.50 ml / min. The data is collected at a data point / second.
    [0161] The CEF column is filled by The Dow Chemical Company with 125 micron + 6% glass beads (MO-CSI Specialty Products) with 1/8 inch stainless tubing. The glass beads are washed with acid by MO-SCI Specialty. The column volume is 2.06 ml. Column temperature calibration is performed using a mixture of NIST Standard Reference Material 1475a polyethylene (1.0 mg / mL) and eicosane (C20H42) (2 mg / mL) in ODCB. The temperature is calibrated by adjusting the elution heating rate, such that the linear polyethylene NIST 1475a has a peak temperature at 101.0 ° C, and the eicosane has a peak temperature of 30.0 ° C. The resolution of the CEF column is calculated with a mixture of NIST 1475a linear polyethylene (1.0 mg / ml) and hexacontane (Fluka, purum,> 97.0%) (1 mg / ml). A baseline separation of hexaconane and polyethylene NIST 1475a is obtained. The hexaconane area (C60Hi22) (from 35.0 to 67.0 ° C) for the NIST 1475a area from 67.0 to 110, 0 ° C, is 50 to 50, and the amount of soluble fraction below 35.0 ° C is <1.8% w / w.
    [0162] The resolution of the CEF column is defined by the following equation: Resolution = (Peak temperature of NIST 1475a - Peak temperature of hexacontane) / (Width at half height of NIST 1475a + Width of half height of Hexacontane) The column resolution is 6.0.
    [0163] The trefBR value is a long chain branch parameter determined from CEF data as described in Yau, Wallace W., "Examples of Using 3D-GPC for Polyolefin Characterization", Macromol. Symp. 2007, 257, 29- 45. trefBR is calculated as:
    where: n = 0.725, LogK = 3.355 for polyethylene
    [0164] The following examples illustrate, but do not limit explicitly or by implication, the present invention. EXPERIMENTATION Representative Polymerization - Two Separate Reaction Zones
    [0165] A continuous high pressure autoclave reactor of "300 mL" was separated into two zones with a deflector (see figure 3), pressurized with ethylene at 193,053 kPa (28,000 psi), at a flow of ethylene of 15 lb / h . Propylene was added to the 3 mole% ethylene stream, based on the total amount of ethylene added to the polymerization process. The resulting mixture was heated to 195 ° C. To the reactor, MMAO cocatalyst and catalyst (CAT A) were added to the first zone, to produce concentrations in the reactor equal to 8.2 molar ppm of Al and 0.016 molar ppm of Zr, each "ppm" was based on the total amount of ethylene added to the polymerization process. The catalyst (CAT A) was zirconium, dimethyl [(2,2 '- [1, 3-propanediilbis (oxyOkO]) (2 -)] -, (OC-6-33) -) (see international publication WO 2007 / 136494 (Cat. All), incorporated in its entirety by reference).
    [0166] The first ethylene-based polymer from the first reactor zone was transferred from the first reactor zone to the second reactor zone, along with ethylene. Peroxide was added to the second zone of the reactor in order to produce a concentration in the second zone of 2.1 molar ppm. Based on the total amount of ethylene added to the polymerization process.
    [0167] The ethylene-based polymer composition was produced at 0.78 lb / h (density = 0.926 g / cm3, melt index (MI or I2) = 1.12 dg / min.). See table 1 (example 2) Table 1
    * Conversion = [(lb ethylene-based polymer composition produced per hour) / (lb ethylene feed per hour) X 100 ★★ MI and density measured in composition containing ppm amounts of stabilizers (1330 ppm IRGANOX 1010 and 670 ppm IRGANOX 168). Representative Polymerization - A Reaction Zone
    [0168] A continuous high pressure autoclave reactor of "300 mL" (see figure 4) was pressurized with ethylene at 193,053 kPa (28,000 psi), at an ethylene flow rate of 12 lb / h. Propylene was added to 1 mol%, based on the total amount of ethylene added to the polymerization process, to the ethylene stream. This mixture was heated to 220 ° C. Peroxide (PO) was added to produce a 1.5 molar ppm concentration in the reactor, based on the total amount of ethylene oxide added to the polymerization process. To the reaction, MMAO and CAT A cocatalysts were added in order to produce concentrations in the reactor of 16.8 molar ppm of Al and 0.071 molar ppm of Zr; each "ppm" was based on the total amount of ethylene added to the polymerization process. A polyethylene composition was produced at 0.72 lb / h of polyethylene (density = 0.9275 g / cm3, melt index (MI or I2) = 1.92 dg / min.). See table 2 (example 7). Table 2 Table 2
    * Conversion = [(lb ethylene-based polymer composition produced per hour) / (lb ethylene feed per hour) X 100 ** MI and density measured in composition containing ppm amounts of stabilizers (1330 ppm IRGANOX 1010 and 670 ppm IRGANOX 168). Examples DSC
    [0169] DSC results for the examples in tables 1 and 2 are shown in table 3 and in figures 5 and 6. Figure 7 shows a plot of the "highest peak melting temperature versus the heat of fusion" for the examples 1-12 in which the example numbers are shown in the figure, compared to the results of WO 2009/114661. Examples 8-9 and Example 12 are of lower density (0.9242 - 0.9264 g / cm3) and were produced in a reaction zone. Table 3 Fusion Temperatures (Tm), Heat of Fusion,% Crystallinity, and Crystallization Temperatures (Tc) from Examples 1-12
    TGDPC (Triple Detector GPC or GPC-3D) of the Examples
    [0170] Examples 1-12 were analyzed by the GPC — 3D technique as described above with results in Table 4 and Figures 8 and 9. The examples show a wide range of properties with weight average molecular weights ranging from 39,540 - 127,730 g / mol, molecular weight distribution of Mw / Mn = 3.88 - 7.81, and Mw (abs) / Mw (gpc) = 11.8 - 4.51, where each linear material has a Mw (abs) / Mw (gpc) ~ 1. Table 4 Triple Detector Gel Permeation Chromatography Results (TGDPC) Examples 1-12
    CEF of Examples
    [0171] The CEF of the examples was summarized in tables 5-6 and figures 10-14. Most examples contain two fractions, one being a high temperature fraction. For examples 2-6 this high temperature fraction was greater than 86 ° C and the trefBR values of this fraction were shown in table 5 for these examples to be 0.73-2.74, indicating long chain branching in the fraction high temperature. For examples 8-11, trefBR was calculated at temperatures above 91 ° C and the trefBR values were 1.93-4.24, indicating long chain branching in the high temperature fraction. Table 5 CEF Results for Examples 1-6
    Table 6 CEF Results for Examples 7-12
    权利要求:
    Claims (16)
    [0001]
    1. Process for forming an ethylene-based polymer composition, characterized by the fact that it comprises at least the following: - Step 1: polymerize a first ethylene-based polymer in the presence of at least one molecular catalyst and a hydrocarbon chain transfer agent , and at a polymerization pressure of at least 96,526 kPa (14,000 psi); - Step 2: polymerize a second polymer based on ethylene; the molecular catalyst being a zirconium complex of a polyvalent aryloxyether corresponding to the formula:
    [0002]
    2. Process according to claim 1, characterized in that the second ethylene-based polymer is polymerized in the presence of a free radical initiator.
    [0003]
    Process according to either of claims 1 or 2, characterized in that the first ethylene-based polymer and the second ethylene-based polymer are polymerized simultaneously.
    [0004]
    Process according to either of claims 1 or 2, characterized in that the first ethylene-based polymer is polymerized first, and the second ethylene-based polymer is polymerized in the presence of the first ethylene-based polymer.
    [0005]
    Process according to any one of claims 1 to 4, characterized in that the molecular catalyst is soluble in supercritical ethylene.
    [0006]
    Process according to any one of claims 1 to 5, characterized in that the first ethylene-based polymer is polymerized in the presence of an alumoxane cocatalyst.
    [0007]
    Process according to any one of claims 1 to 6, characterized in that the free radical initiator is a peroxide.
    [0008]
    Process according to any one of claims 1 to 7, characterized in that the polymerization temperature in Step 1 is greater than, or equal to, 195 ° C.
    [0009]
    9. Process according to any of claims 1 to 8, characterized in that no hydrogen is added in Step 1 or Step 2.
    [0010]
    Process according to any one of claims 1 to 9, characterized in that the process additionally comprises polymerizing a third polymer based on ethylene.
    [0011]
    11. Process according to any one of claims 1 to 10, characterized by the fact that at least one aluminum alkyl is added to the process after Step 2.
    [0012]
    12. Process according to any one of claims 1 to 11, characterized in that at least one polyalkylene glycol is added to the process after Step 2.
    [0013]
    13. Polymer composition, characterized by the fact that it is formed by the process, as defined in any one of claims 1 to 12.
    [0014]
    14. Polymer composition according to claim 13, characterized in that the polymer composition has a fraction by CEF, at a temperature of at least 85 ° C, of at least 5 weight percent (based on the weight of the polymer composition), and which has a trefBr value greater than 0.5.
    [0015]
    15. Composition, characterized by the fact that it comprises the polymer composition as defined in any of claims 13 or 14, and at least one additive.
    [0016]
    16. Article, characterized by the fact that it comprises at least one component formed from the composition defined in any one of claims 13 to 15.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB1205635A|1967-05-12|1970-09-16|Ici Ltd|Polymerisation of ethylene|
    FR2519007B1|1981-12-24|1985-12-27|Charbonnages Ste Chimique|MODIFIED COPOLYMERS OF ETHYLENE AND AT LEAST ONE A-OLEFIN AND PROCESS FOR THEIR PREPARATION|
    JPS629601B2|1982-07-29|1987-03-02|Sumitomo Chemical Co|
    US5084534A|1987-06-04|1992-01-28|Exxon Chemical Patents, Inc.|High pressure, high temperature polymerization of ethylene|
    GB9103527D0|1991-02-20|1991-04-10|Exxon Chemical Patents Inc|Hp catalyst killer|
    US5272236A|1991-10-15|1993-12-21|The Dow Chemical Company|Elastic substantially linear olefin polymers|
    US5278272A|1991-10-15|1994-01-11|The Dow Chemical Company|Elastic substantialy linear olefin polymers|
    US6545088B1|1991-12-30|2003-04-08|Dow Global Technologies Inc.|Metallocene-catalyzed process for the manufacture of EP and EPDM polymers|
    DE69211569T2|1991-12-30|1997-01-23|Dow Chemical Co|ETHYLENE INTERPOLYMER POLYMERIZATION|
    BR9405715A|1993-01-29|1995-11-28|Dow Chemical Co|Process for preparing an ethylene / a-olefin interpolymer composition and ethylene / a-olefin interpolymer composition|
    US6448341B1|1993-01-29|2002-09-10|The Dow Chemical Company|Ethylene interpolymer blend compositions|
    GB9319340D0|1993-09-17|1993-11-03|Exxon Chemical Patents Inc|Olefin polymersisation process|
    US5616664A|1994-08-02|1997-04-01|The Dow Chemical Company|Polymerization process with biscyclopentadienyl diene complex containing catalysts|
    IT1275777B1|1995-07-06|1997-10-17|Enichem Spa|METALLOCENIC CATALYST FOR THE POLYMERIZATION OF OLEFINS|
    US5869575A|1995-08-02|1999-02-09|The Dow Chemical Company|Ethylene interpolymerizations|
    WO1999045042A1|1998-03-04|1999-09-10|Exxon Chemical Patents Inc.|Noncoordinating anions for olefin polymerization|
    US6897276B2|2002-04-24|2005-05-24|Symyx Technologies, Inc.|Bridged bi-aromatic ligands, catalysts, processes for polymerizing and polymers therefrom|
    JP4158424B2|2002-06-04|2008-10-01|東ソー株式会社|Ethylene polymer and process for producing the same|
    WO2006049783A1|2004-11-02|2006-05-11|Dow Global Technologies Inc.|Process for producing low density polyethylene compositions and polymers produced therefrom|
    CN101356006B|2005-12-16|2013-01-30|陶氏环球技术有限责任公司|Polydentate heteroatom ligand containing metal complexes, catalysts and methods of making and using the same|
    WO2007136495A2|2006-05-17|2007-11-29|Dow Global Technologies Inc.|High efficiency solution polymerization process|
    KR101141494B1|2007-09-05|2012-05-03|에스케이이노베이션 주식회사|Ethylene copolymer having multiple pitch in molecular weight distribution and the method of preparing the same|
    WO2009114661A1|2008-03-13|2009-09-17|Dow Global Technologies Inc.|Long chain branched , block or interconnected copolymers of ethylene in combination with one other polymer|
    BRPI1007573A2|2009-06-05|2019-09-24|Dow Global Technlogies Inc|process|
    US8722817B2|2009-06-05|2014-05-13|Dow Global Technologies Llc|Process to make long chain branched , block, or interconnected copolymers of ethylene|
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    US8440772B2|2011-04-28|2013-05-14|Chevron Phillips Chemical Company Lp|Methods for terminating olefin polymerizations|ES2674169T3|2010-05-28|2018-06-27|Basell Polyolefine Gmbh|Polyethylene composition and method to obtain it|
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    US9527940B2|2012-12-27|2016-12-27|Dow Global Technologies Llc|Polymerization process for producing ethylene based polymers|
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    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-08-13| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-01-21| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2020-06-30| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-11-10| 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 21/11/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    2021-09-14| B21F| Lapse acc. art. 78, item iv - on non-payment of the annual fees in time|Free format text: REFERENTE A 10A ANUIDADE. |
    2022-01-04| B24J| Lapse because of non-payment of annual fees (definitively: art 78 iv lpi, resolution 113/2013 art. 12)|Free format text: EM VIRTUDE DA EXTINCAO PUBLICADA NA RPI 2645 DE 14-09-2021 E CONSIDERANDO AUSENCIA DE MANIFESTACAO DENTRO DOS PRAZOS LEGAIS, INFORMO QUE CABE SER MANTIDA A EXTINCAO DA PATENTE E SEUS CERTIFICADOS, CONFORME O DISPOSTO NO ARTIGO 12, DA RESOLUCAO 113/2013. |
    优先权:
    申请号 | 申请日 | 专利标题
    US41956010P| true| 2010-12-03|2010-12-03|
    US61/419,560|2010-12-03|
    PCT/US2011/061622|WO2012074812A1|2010-12-03|2011-11-21|Processes to prepare ethylene-based polymer compositions|
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