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    • 专利摘要:
    composition comprising an ethylene-based polymer and article. a polymer based on ethylene, which is a low density polyethylene (ldpe), obtained through the polymerization of the free radical of ethylene, and the ldpe has a parameter gpc '' lsp '' less than 1.60. an ethylene-based polymer which comprises the following characteristics: (a) at least 0.1 amyl group per 1000 total carbon atoms; (b) a melt index of 0.01 to 0.3; (c) an average molecular weight z of mz (conv) greater than 350,000 g / mol and less than 425,000 g / mol; (d) a gpcbr value of 1.50 to 2.05; and (e) a mwd (conv) [mw (conv) / mn (conv)] from 6 to 9. an ethylene-based polymer that comprises the following characteristics: (a) at least 0.1 amyl group per 1000 total carbon atoms; (b) a melt viscosity ratio (v0.1 / v100), at 190 ° c, greater than, or equal to, 58; (c) a melt viscosity of 0.1 rad / s, 190 ° c, greater than, or equal to, 40,000 pa * s; and (d) a gpcbr value of 1.50 to 2.25.
    公开号:BR112015006812B1
    申请号:R112015006812-0
    申请日:2013-03-13
    公开日:2021-03-23
    发明作者:Teresa P. Karjala；Lori L. Kardos；Wallace W. Yau；Jose Ortega；Alfred E. Vigil
    申请人:Dow Global Technologies Llc；
    IPC主号:
    专利说明:

    [0001] [0001] Blown film production lines are typically limited in productivity due to bubble stability. Linear mixed low density polyethylene (LLDPE) with 0.5% by weight - 90% by weight of low density polyethylene (LDPE) increases bubble stability, partly due to the greater resistance to LDPE melting. The increase in melt resistance in part provides an increase in the productivity of the film. However, very high melt strength can cause gels and poor film quality, as well as the ability to lift the potential limitation for thinner thickness gauges (0.5 to 1 mil film). High melt strength resins also typically have reduced optical properties and reduced toughness. Thus, there is a need for new ethylene-based polymers, such as LDPEs, which have an optimized balance of melt strength and improved mechanical and optical properties of the film, for blowing film applications.
    [0002] [0002] LDPE polymers are described in the following references: WO 2010/042390, WO 2010/144784, WO 2011/019563, WO 2012/082393, WO 2006/049783, WO 2009/114661, US 2008/0125553, US 7741415 , and EP 2239283B1. However, these polymers do not provide an optimized balance of improved mechanical properties of the film and high melt resistance for blowing film applications. Thus, as discussed above, there remains a need for new ethylene-based polymers, such as LDPEs, that have an optimized balance of melt strength, optics, processability, and productivity, and toughness. These needs and others were found by the following invention. Summary of the invention
    [0003] [0003] The invention provides a composition comprising an ethylene-based polymer, which is a low density polyethylene (LDPE), obtained by the free radical polymerization of ethylene, and LDPE has a lower “LSP” GPC parameter that 1.60.
    [0004] (a) pelo menos 0,1 grupo amila por 1000 átomos de carbonos totais; (b) um índice de fundido de 0,01 a 0,3; (c) um peso molecular médio z de Mz (conv) maior que 350,000 g/mol e menor que 425,000 g/mol; (d) um valor gpcBR de 1,50 a 2,05; e (e) um MWD (conv) [MW(conv)/Mn(conv)] de 6 a 9. [0004] The invention also provides a composition comprising an ethylene-based polymer that comprises the following characteristics: (a) at least 0.1 amyl group per 1000 total carbon atoms; (b) a melt index of 0.01 to 0.3; (c) an average molecular weight z of Mz (conv) greater than 350,000 g / mol and less than 425,000 g / mol; (d) a gpcBR value of 1.50 to 2.05; and (e) a MWD (conv) [MW (conv) / Mn (conv)] from 6 to 9.
    [0005] (a) pelo menos 0,1 grupo amila por 1000 átomos de carbonos totais; (b) uma proporção de viscosidade de fundido (V0,1/V100), a 190°C, maior que, ou igual a, 58; (c) uma viscosidade de fundido em 0,1 rad/s, 190°C, maior que, ou igual a, 40,000 Pa*s; e (d) um valor gpcBR de 1,50 a 2,25. [0005] The invention also provides a composition comprising an ethylene-based polymer that comprises the following characteristics: (a) at least 0.1 amyl group per 1000 total carbon atoms; (b) a melt viscosity ratio (V0.1 / V100), at 190 ° C, greater than, or equal to, 58; (c) a melt viscosity at 0.1 rad / s, 190 ° C, greater than, or equal to, 40,000 Pa * s; and (d) a gpcBR value of 1.50 to 2.25.
    [0006] [0006] Figure 1 represents a GPC-LS (light scattering) profile of Example 1;
    [0007] [0007] Figure 2 represents a GPC-LS (light scattering) profile of Example 2;
    [0008] [0008] Figure 3 represents a GPC-LS (light scattering) profile of Comparative Example 1; and
    [0009] [0009] Figure 4 represents a block diagram of the reaction system of the process used to produce the Examples of the invention. Detailed description of the invention
    [0010] [0010] The new ethylene-based polymers, such as LDPEs, were developed with optimized melt resistance to increase processability and production; allow drawability for thin gauges; minimize gels when mixed with other polymers, and improve toughness relative to current LDPE products.
    [0011] [0011] As discussed above, in a first aspect, the invention provides a composition comprising a low density polyethylene (LDPE) obtained by free radical polymerization of, and the LDPE having a light scattering parameter GPC "LSP" less than 1.60.
    [0012] [0012] The composition can comprise a combination and two or more embodiments as described here.
    [0013] [0013] LDPE can comprise a combination of two or more embodiments described here.
    [0014] [0014] In one embodiment, LDPE has a GPC light diffusion parameter "LSP" less than 1.50, additionally less than 1.40 and additionally less than 1.35.
    [0015] [0015] In one embodiment, LDPE has a GPC light diffusion parameter "LSP" from 0.1 to 1.6, in addition, from 0.3 to 1.4 and, in addition, from 0.9 to 1, two.
    [0016] [0016] In one embodiment, LDPE has at least 0.1 amyl group per 1000 carbon atoms.
    [0017] [0017] In one embodiment, LDPE has a gpcBR value of 1.50 to 2.25.
    [0018] [0018] In one embodiment, LDPE has a viscosity ratio (V0.1 / V100, at 190 ° C) greater than, or equal to 50, additionally greater than, or equal to 52.
    [0019] (a) pelo menos 0,1 grupo amila por 1000 átomos de carbonos totais; (b) um índice de fundido de 0,01 a 0,3; (c) um peso molecular médio z de Mz (conv) maior que 350,000 g/mol e menor que 425,000 g/mol; (d) um valor gpcBR de 1,50 a 2,05; e (e) um MWD (conv) [MW(conv)/Mn(conv)] de 6 a 9. [0019] In a second aspect, the invention provides a composition comprising an ethylene-based polymer that comprises the following characteristics (a) at least 0.1 amyl group per 1000 total carbon atoms; (b) a melt index of 0.01 to 0.3; (c) an average molecular weight z of Mz (conv) greater than 350,000 g / mol and less than 425,000 g / mol; (d) a gpcBR value of 1.50 to 2.05; and (e) a MWD (conv) [MW (conv) / Mn (conv)] from 6 to 9.
    [0020] (a) pelo menos 0,1 grupo amila por 1000 átomos de carbonos totais; (b) uma proporção de viscosidade de fundido (V0,1/V100), a 190°C, maior que, ou igual a, 58; (c) uma viscosidade de fundido em 0,1 rad/s, 190°C, maior que, ou igual a, 40,000 Pa*s; e (d) um valor gpcBR de 1,50 a 2,25. [0020] In a third aspect, the invention provides a composition comprising an ethylene-based polymer that comprises the following characteristics: (a) at least 0.1 amyl group per 1000 total carbon atoms; (b) a melt viscosity ratio (V0.1 / V100), at 190 ° C, greater than, or equal to, 58; (c) a melt viscosity at 0.1 rad / s, 190 ° C, greater than, or equal to, 40,000 Pa * s; and (d) a gpcBR value of 1.50 to 2.25.
    [0021] [0021] The following embodiments apply to the second and third aspects (compositions) of the invention.
    [0022] [0022] The composition can comprise a combination of two or more embodiments as described here.
    [0023] [0023] The ethylene-based polymer can comprise a combination of two or more embodiments as described here.
    [0024] [0024] In one embodiment, the ethylene-based polymer has a light diffusion parameter GPC - "LSP" less than 2.0.
    [0025] [0025] In one embodiment, the polymer has a proportion and viscosity (V0.1 / V100, at 190 ° C) greater than or equal to 50, additionally greater than or equal to 52.
    [0026] [0026] The following embodiments apply to all three aspects (compositions) of the invention.
    [0027] [0027] In one embodiment, the polymer has a MWD (conv.) Of 5 to 8.
    [0028] [0028] In one embodiment, the polymer has a melt resistance (MS) greater than 15 cN and less than 25 cN.
    [0029] [0029] In one embodiment, the polymer has a melt resistance of at least 15 cN and less than 21 cN, and a breaking speed greater than 40 mm / s.
    [0030] [0030] In one embodiment, the polymer has a viscosity ratio (V0.1 / V100), at 190 ° C) greater than, or equal to 50, additionally greater than, or equal to 55, additionally greater than, or equal to 59, in addition, greater than, or equal to 60.
    [0031] [0031] In one embodiment, the polymer has a MWD (conv) greater than 6.
    [0032] [0032] In one embodiment, the polymer has a melting viscosity at 0.1 rad / s, 190 ° C, greater than or equal to 42,000 Pa * s, additionally greater than, or equal to 45,000 Pa * s.
    [0033] [0033] In one embodiment, the polymer has a density of 0.910 to 0.940 g / cc, additionally 0.910 to 0.930 g / cc, additionally 0.915 to 0.925 g / cc, and additionally 0.916 to 0.922 g / cc (1 cc = 1 cm3).
    [0034] [0034] In one embodiment, the polymer has a cc-GCP Mw of 75,000 g / mol to 175,000 g / mol, additionally from 100,000 to 150,000 g / mol and, in addition, from 115,000 g / mol to 140,000 g / mol.
    [0035] [0035] In one embodiment, the polymer has a cc-GCP Mz of 300,000 to 500,000 g / mol, in addition from 350,000 g / mol to 450,000 g / mol and, in addition, from 375,000 g / mol to 425,000 g / mol.
    [0036] [0036] In one embodiment, the polymer has an Mw-abs of 200,000 to 350,000 g / mol, in addition from 225,000 g / mol to 325,000 g / mol and, in addition, from 250,000 g / mol to 300,000 g / mol.
    [0037] [0037] In one embodiment, the polymer has an Mw (LSabs) / Mw (cc-GPC) of 1 to 3, additionally 1.5 to 2.75, and additionally 1.9 to 2.4.
    [0038] [0038] In one embodiment, the polymer has an IVw of 1.00 dl / ga 1.30 dl / g, additionally 1.05 dl / ga 1.25 dl / g, and additionally 1.1 dl / ga 1.2 dl / g.
    [0039] [0039] In one embodiment, the polymer has an IVcc of 1.4 dl / g to 2.5 dl / g, additionally 1.6 dl / g to 2.25 dl / g, and additionally 1.7 -2, 1 dl / g.
    [0040] [0040] In one embodiment, the polymer has an IVcc / IVw of 1.2 dl / g to 2.2 dl / g, in addition to 1.4 dl / g to 1.9 dl / g, and additionally to 1.6 dl / ga 1.7 dl / g.
    [0041] [0041] In one embodiment, the polymer has more than, or equal to 0.2 amyl groups (branches) per 1000 carbon atoms, more than, or equal to 0.5 amyl groups per 1000 carbon atoms, additionally more than that, or equal to, 1 amyl group per 1000 carbon atoms, and additionally more than, or equal to 1.4 amyl groups per 1000 carbon atoms.
    [0042] [0042] In one embodiment, the polymer has a rheological ratio (V0.1 / V100), at 190 ° c, from 40 to 80, additionally from 45 to 70, and additionally from 50 to 65.
    [0043] [0043] In one embodiment, the polymer has a delta-tan (measured at 0.1 rad / s at 190 ° C) less than, or equal to 2.0, additionally less than, or equal to 1.75, and additionally greater that, or equal to 1.50.
    [0044] [0044] In one embodiment, the polymer has a tan delta (measured at 0.1 rad / s) from 0.5 to 2, in addition to 0.75 to 1.75, and additionally from 1 to 1.5.
    [0045] [0045] In one embodiment, the polymer has a viscosity of 0.1 rad / s and 190 ° C of 30,000 Pa * s to 80,000 Pa * s, in addition to 40,000 Pa * s to 70,000 Pa * s, and in addition to 45,000 Pa * s to 60,000 Pa * s.
    [0046] [0046] In one embodiment, the polymer is formed in a higher pressure polymerization process (P greater than 100 MPa).
    [0047] [0047] In one embodiment, the polymer is a low density polyethylene (LDPE), obtained through a high pressure free radical polymerization (P greater than 100 mPa), of ethylene.
    [0048] [0048] In one embodiment, the polymer is a low density polyethylene (LDPE).
    [0049] [0049] In one embodiment, the polymer is a low density polyethylene (LDPE).
    [0050] [0050] In one embodiment, the polymer is present in more than, or equal to, 10 weight percent, based on the weight of the composition.
    [0051] [0051] In one embodiment, the polymer is present in an amount of 10 to 50 weight percent, in addition to 20 to 40 weight percent, based on the weight of the composition.
    [0052] [0052] In one embodiment, the polymer is present in an amount of 60 to 90 weight percent, in addition to 65 to 85 weight percent, based on the weight of the composition.
    [0053] [0053] In one embodiment, the polymer is present in an amount of 1 to 10 weight percent, in addition, from 1.5 to 5 weight percent, based on the weight of the composition.
    [0054] [0054] In one embodiment, the composition further comprises another polymer based on ethylene. Other suitable ethylene-based polymers include, but are not limited to, DOWFLE Polyethylene Resins, TUFLIN Linear Low Density Polyethylene Resins, ELITE or ELITE AT Enhanced Polyethylene Resins (all available from The Dow Chemical Company), polyethylene high density (d ≥ 0.96 g / cc), medium density polyethylene (density 0.935 to 0.955 g / cc), EXCEED polymers and ENABLE polymers (both from ExxonMobil), LDPE, and EVA (ethylene vinyl acetate) .
    [0055] [0055] In one embodiment, the composition further comprises another ethylene-based polymer that differs in one or more properties, such as density, melt index, comonomers, comonomer content, etc., from the polymer of the invention. Other suitable ethylene-based polymers include, but are not limited to, DOWLEX polyethylene resins (LLDPEs), TUFLIN linear low density polyethylene resins, ELITE or ELITE AT enhanced polyethylene resins (all available from “The Dow Chemical Company”) , high density polyethylene (d> 0.96 g / cc), medium density polyethylene (density 0.935 to 0.955 g / cc), EXCEED polymers and ENABLE polymers (both from ExxonMobil), LDPE and EVA (ethylene vinyl acetate ).
    [0056] [0056] In one embodiment, the composition further comprises a polymer based on propylene. Suitable propylene-based polymers include polypropylene homopolymers, propylene / α-olefin interpolymers, and propylene / ethylene interpolymers.
    [0057] [0057] In one embodiment, the composition further comprises a branched ethylene / α-olefin interpolymer and, preferably, a heterogeneously branched ethylene / α-olefin copolymer. In one embodiment, the heterogeneously branched ethylene / α-olefin interpolymer, and preferably, a heterogeneously branched ethylene / α-olefin copolymer has a density of 0.89 to 0.95 g / cc, in addition to 0.90 to 0, 93 g / cc. In a further embodiment, the composition comprises from 1 to 99 weight percent, in addition from 15 to 85 weight percent, of the ethylene-based polymer of the invention, based on the weight of the composition.
    [0058] [0058] In one embodiment, the composition comprises less than 5 ppm, additionally less than 2 ppm, additionally less than 1 ppm, and additionally less than 0.5 ppm of sulfur, based on the weight of the composition.
    [0059] [0059] In one embodiment, the composition does not contain sulfur.
    [0060] [0060] In one embodiment, the composition comprises from 1.5 to 80 weight percent of a polymer of the invention. In a further embodiment, the composition further comprises an LLDPE (linear low density polyethylene).
    [0061] [0061] In one embodiment, the composition comprises from 1.5 to 20 weight percent of a polymer of the invention. In a further embodiment, the composition further comprises an LLDPE.
    [0062] [0062] In one embodiment, the composition comprises from 20 to 80 weight percent, in addition from 50 to 80 weight percent of the polymer of the invention. In one embodiment, the composition additionally comprises an LLDPE.
    [0063] [0063] A composition of the invention can comprise a combination of two or more embodiments as described here.
    [0064] [0064] In one embodiment, for the first and third aspects, the polymer has a melt index (I2) of 0.01 to 10 g / 10 minutes, additionally 0.05 to 5g / 10 minutes and additionally, 0.05 to 0.5g / 10 minutes.
    [0065] [0065] In one embodiment, for the first and third aspects, the polymer has a melting index (I2) of 0.001 to 1.5 g / 10 minutes, in addition to 0.05 to 1.0 g / 10 minutes, and additionally 0.05 to 0.25 g / 10 minutes.
    [0066] [0066] In one embodiment, for the first and the third aspect, the polymer has a melt index (I2) of 0.01 to 1g / 10 minutes.
    [0067] [0067] In one embodiment, for the first and third aspects, the polymer has a melting index (I2) less than or equal to 0.5.
    [0068] [0068] In one embodiment, for the first and third aspects, the polymer has a rheology ratio (V0.1 / V100) ,, at 190 ° C, greater than, or equal to 40, additionally greater than, or equal to 45, in addition greater than, or equal to 50, and additionally greater than, or equal to 55.
    [0069] [0069] The invention also provides an article comprising at least one component formed from a composition of the invention. In a further embodiment, the article is a film. In another embodiment, the article is a coating.
    [0070] [0070] The invention also provides a process for forming an ethylene-based polymer of the invention from any of the previously described embodiments, the process comprising polymerisation ethylene and, optionally, at least one comonomer, in at least one reactor of autoclave.
    [0071] [0071] The invention also provides a process for forming a polymer of any prior embodiment, the process comprising the polymerization of ethylene and, optionally, at least one comonomer, in at least one tubular reactor.
    [0072] [0072] The invention also provides a process for forming an ethylene-based polymer of the invention from any of the previously described embodiments, the process comprising polymerisation ethylene, and optionally, at least one comonomer, in a combination of at least one tubular reactor in at least one autoclave reactor.
    [0073] [0073] The composition of the invention can comprise a combination of two or more embodiments as described herein.
    [0074] [0074] The ethylene-based polymer can comprise a combination of two or more embodiments as described here.
    [0075] [0075] An inventive article may comprise a combination of two or more embodiments as described here. An inventive film can comprise a combination of two or more embodiments as described here.
    [0076] [0076] A process of the invention can comprise a combination and two or more embodiments as described here. Process
    [0077] [0077] For the production of an ethylene-based polymer, including an LDPE of the invention, a polymerization process initiated in a high pressure free radical is typically used. Two types of different polymerization processes initiated by high pressure free radicals are known. In the first type, a stirred autoclave container having one or more zones is used. The autoclave reactor usually has several injection points for the initiator or for the monomer feed, or both. In the second type, a tube involved is used as a reactor, which has one or more reaction zones. Appropriate, but not limiting, the length of the reactor can be from 100 to 3000 meters (m), or from 1000 to 2000 meters. The start of a reaction zone for both types of reactor is typically defined by the lateral injection of both the reaction initiator, ethylene, chain transfer agent (or telomer), comonomers, as well as any combination thereof. A high pressure process can be carried out in an autoclave or in tubular reactors, each having one or more reaction zones, or in a combination and autoclave and tubular reactors, each comprising one or more reaction zones.
    [0078] [0078] A chain transfer agent can be used to control molecular weight. In a preferred embodiment, one or more chain transfer agents (CTAs) are added in a polymerization process of the invention. Typical CTAs that can be used include, but are not limited to, propylene, isobutene, n-butene, 1-butene, methyl ethyl ketone, acetone, and propionaldehyde. In one embodiment, the amount of CTA used in the process is 0.03 to 10 weight percent of the total reaction mixture.
    [0079] [0079] The ethylene used for the production of the ethylene-based polymer can be purified ethylene, which is obtained by removing the polar components from a loop recycling stream, or by using a configuration in the reaction system, so that only fresh ethylene is used to make the polymer of the invention. It is not typical that only purified ethylene is required to make the polymer based on ethylene. In such cases, ethylene from the recycling loop can be used.
    [0080] [0080] In one embodiment, the ethylene-based polymer is a polyethylene homopolymer.
    [0081] [0081] In another embodiment, the ethylene-based polymer comprises ethylene and one or more comonomers and, preferably, a comonomer. Comonomers include, but are not limited to, alpha-olefin comonomers, typically having no more than 20 carbon atoms. For example, α-olefin comonomers can have 3 to 10 carbon atoms, in addition, 3 to 8 carbon atoms. Examples of 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. In an alternative, exemplary comonomers include, but are not limited to, C3-C8 α, β-unsaturated carboxylic acids (eg, maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid), crotonic acid derivatives C3-C8 α, β-unsaturated carboxylics (for example, unsaturated C3-C15 carboxylic acid esters, in particular, C1-C6 alkanyl ester, or anhydrides), methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, methyl 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. Additions
    [0082] [0082] A composition of the invention can comprise one or more additives. Additives include, but are not limited to, stabilizers, plasticizers, antistatic agents, pigments, dyes, nucleating agents, fillers, glidants, flame retardants, processing aids, smoke inhibitors, viscosity control agents, and anti-blocking agents. The polymeric composition can, for example, comprise less than 10 percent (by combined weight) of one or more additives, based on the weight of the polymeric composition of the invention.
    [0083] [0083] In one embodiment, the polymers of this invention are treated with one or more stabilizers, for example, antioxidants, such as IRGANOX 1010, IRGANOX 1076 and IRGAFOS 168 ("Ciba specialty Chemicals; Glattbrugg, Switzerland"). In general, polymers are treated with one or more stabilizers before extrusion or another melting process. Processing aids such as plasticizers include, but are not limited to, phthalate, such as phthalate and dioctyl and phthalate and diisobutyl, natural oils such as lanolin, and paraffin, naphthenic and aromatic oils obtained from petroleum refining, and liquid resins obtained from rosine or petroleum raw material. Examples of oil classes, useful as processing aids include, white mineral oil such as KAYDOL oil (Chemtura Corp .; Middlebury, Conn.) And SHELLFLEX 371 naphthenic oils (Shell Lubricants; Huston, Texa). Another suitable oil is TUFFLO oil (Lyondell Lubricants; Huston, Texas).
    [0084] [0084] The combinations and mixtures of the polymers of the invention with other polymers can be carried out. Polymers suitable for combination with the polymer of the invention include natural and synthetic polymers. Exemplary polymers for mixing include propylene-based polymers (both, impact-modifying polypropylene, isotactic polypropylene, atactic polypropylene, and random ethylene / propylene copolymers), various types of ethylene-based polymers, including high free radical LDPE pressure, LLDPE prepared with Ziegler-Natta catalysts, PE prepared with single site catalysts, including multiple reactor PE (“reactor mixtures” of PE Ziegler-Natta and PE catalyzed at a single site, such as products described in the northern patent American 6,545,088 (Kolthammer et al.); US 6,538,070 (Cardwell, etl); US 6,566,446 (parikh, et al.); US 5,844,045 (Kolthammer et al.); US 5,869,575 (Kolthammer et al.); and US 6,448,341 (Kolthammer et al.)), EVA, ethylene / vinyl alcohol copolymers, polystyrene, impact modifier polystyrene, ABS, styrene / butadiene block copolymers, and hydrogenated derivatives thereof (SBS and SEBS), and thermoplastic polyurethanes waistband. Homogeneous polymers, such as olefin plastomers and elastomers, ethylene and propylene-based copolymers (for example, polymers available under the trade name VERSIFY PLastomers & Elastomers (The Dow Chemical Company) and VISTAMAXX (ExxonMobil Chemical Co.) can also be useful as a component in the combination comprising the polymer of the invention. applications
    [0085] [0085] The polymers of this 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 rotomolded articles, coatings, fibers, and non-woven fabrics and fabrics.
    [0086] [0086] A polymer of the invention can be used in a variety of films, including, but not limited to, extrusion coating, food packaging, consumer goods, in industry, agriculture (applications or films), laminating films, films for fresh cut products, meat films, cheese films, sweet films, sharpness-reducing films, adhesion-reducing films, extension films, silage films, greenhouse films, fumigation films, coating films, extendable film ( “Stretch hood”), high capacity transport bags, for animal feed, sandwich bags, sealants, and external diaper cover.
    [0087] [0087] A polymer of the invention is also useful in order to direct its final application. A polymer of the invention can be used for wire and cable coating operations, in sheet extrusion for vacuum forming operations, and forming molded articles, including the use of injection molding, blow molding processes, or molding processes. rotomoulding.
    [0088] [0088] Other applications suitable for the polymers of the invention include, elastic films and fibers; soft-touch products, such as appliance handles; gaskets and profiles; internal parts of vehicles and profiles; foam products (both open cell and closed cell); impact modifiers for other thermoplastic polymers, such as high density polyethylene; or other olefin polymers; cover coatings, and flooring. Definitions
    [0089] [0089] The term "polymer", as used here refers to a polymeric compound prepared through polymerisation monomers, whether of the same or a different type. The generic term, polymer, thus encompasses the term homopolymer (used to refer to polymers prepared from only one type of monomer, with the understanding that trace amounts of impurities can be incorporated within the polymeric structure), and the interpolymer term, as defined below. The trace amounts of impurities can be incorporated into and / or within a polymer.
    [0090] [0090] The term "interpolymer" as used here refers to polymers prepared by the polymerization of at least two different types of monomers. The generic term interpolymer includes copolymers (used to refer to polymers prepared from two different types of monomers), and polymers prepared from more than two different types of monomers.
    [0091] [0091] The term "ethylene-based polymer" as used herein refers to a polymer that comprises a majority amount of polymerized ethylene monomer (based on the weight of the polymer) and, optionally, can contain at least one comonomer.
    [0092] [0092] The term "ethylene / α-olefin interpolymer" as used here, refers to an interpolymer comprising a majority of polymerized ethylene monomer (based on the weight of the interpolymer) and at least one α-olefin.
    [0093] [0093] The term "ethylene / α-olefin copolymer" as used here, refers to a copolymer that comprises a majority amount of polymerized ethylene monomer (based on the weight of the copolymer), and an α-olefin, as the only of two types of monomers.
    [0094] [0094] The term "propylene-based polymer" as used here, refers to a polymer that comprises a majority of polymerized propylene monomers (based on the weight of the polymer) and, optionally, can comprise at least one comonomer.
    [0095] [0095] The term "composition" as used here, includes a mixture of materials comprising the composition, as well as reaction products and decomposition products formed from the materials of the composition.
    [0096] [0096] The term "combination" or "combination and polymer", as used here, refers to a mixture of two or more polymers. A combination may or may not be miscible (without a separate phase at the molecular level). A combination may or may not be in separate phases. A combination 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. The combination can be carried out by physically mixing two or more polymers at the macro level (for example, melt or compost mixing resins) or at the micro level (for example, simultaneous formation within the same reactor).
    [0097] [0097] The terms "comprising", "including", "having", and their derivatives, are not intended to exclude the presence of any additional component, step or procedure, whether or not it is specifically described. In order to avoid any doubt, all compositions claimed through the use of the term "comprising" may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless stated otherwise. In contrast, the term “essentially consisting of” excludes from the scope of any subsequent quotation any other component, step or procedure, except those that are not essential to operability. The term “consisting of” excludes any component, step or procedure not specifically outlined or listed. Testing methods Density: samples for measuring density were prepared according to ASTM D 4703-10. The samples were pressed at 374 ° F (190 ° C) for five minutes at 10,000 psi (68 MPa). The temperature was maintained at 374 ° F (190 ° C) for a further five minutes, and then the pressure was increased to 30,000 psi (207 MPa) for three minutes. This was followed by one minute maintaining at 70 ° F (21 ° C) and 30,000 psi (207 MPa). Measurements were made within one hour of sample processing using ASTM D792-08, Method B. Melting index:
    [0098] [0098] The melting index, or I2, was measured according to ASTM D 1238-10, condition of 190 ° C / 2.16 Kg, Method A, and was recorded in grams eluted for 10 minutes. Nuclear Magnetic Resonance (13C NMR)
    [0099] [0099] The samples were prepared by adding approximately “3g of a 50/50 mixture of tetrachloreoethanod2 / orthodichlorobenzene, containing 0.025M Cr (AcAc) 3”, to a “0.25 to 0.40g of polymeric sample”, in a 10 mm NMR tube. Oxygen was removed from the sample by placing the tube opening in a nitrogen medium for at least 45 minutes. The samples were then dissolved and homogenized by heating the tube, and its contents at 150 ° C, using a heating block and heat gun. Each dissolved sample was visually prior to analysis, and was not allowed to cool before insertion into the heated NMR sample holders.
    [0100] [0100] All data was collected using a 400 MHz Bruker spectrometer. Data were acquired using a six-second delay repetition pulse, 90 degree flip angles, and reverse portal decoupling, with a sample temperature of 125 ° C. All measurements were made on a non-woven sample in a locked fashion. The samples were allowed to thermally equilibrate for seven minutes before data acquisition. The chemical structure of 13C NMR was internally referred to as 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 chains. The peak of 32.2 ppm, representing the third carbon at 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:
    [0101] [0101] Samples were prepared by adding approximately 130 mg of sample to “3.25 g of 50/50, by weight of tetrachloroethane-d2 / perchloroethane” with 0.001 M Cr (AcAc) 3 in a 10 µM NMR tube mm NORELL 1001-7. The samples were purged by bubbling N2 through the solvent, via a pipette inserted into the tube, for approximately five minutes, to prevent oxidation. Each tube was capped, sealed with TEFLON tape, and then saturated at room temperature, overnight, to facilitate sample dissolution. The samples were kept in an N2 purge box, during storage, before and after preparation, to minimize O2 exposure. The samples were heated and vortexed at 115 ° C to ensure homogeneity. Parameters for data acquisition
    [0102] [0102] The 1H NMR was performed on a 400 MHz Bruker AVANCE spectrometer, equipped with a Bruker Dual DUL high temperature Cryoprobe and a sample temperature of 120 ° C. Two experiments were carried out to obtain the spectrum, a control spectrum to quantify the total protons of the polymer, and a double-pressaturation experiment, which suppressed the intense peaks of the polymer main chain, and enabled the high sensitivity of the spectrum to quantify the final groups. . The control was run with a ZG pulse, 4 sweeps, SWH 10,000 Hz, AQ 1.64s, D1 14 s. The double presaturation experiments were run with a modified pulse sequence, TD 32768, 100 scans, DS 4, SWH 10,000 Hz, AQ 1.64 s, D1 1 s, D13 13s. Data analysis - Calculation of 1H NMR:
    [0103] [0103] The residual 1H signal in 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 signal from all over the polymer in the control experiment. For the pressaturation experiment, the TCE signal was also adjusted to 100, and the corresponding integrals for unsaturation (vinylene at about 5.40 to 5.60 ppm, tri-substituted 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.
    [0104] [0104] In the spectrum of the pressaturation experiment, the regions for cis and trans-vinylene, tri-substituted, vinyl, and vinylidene have been integrated. The integral of the whole polymer of the control experiment was divided by two, to obtain a representative value of X thousand carbons (that is, if the polymer integral = 28,000, this represents 14,000 carbons, and x = 14).
    [0105] [0105] The integral unsaturated group, divided by the corresponding number of protons contributing to that integral, represents the moles of each type of unsaturation per X thousand carbons. Dividing the moles of each type of unsaturation by X, then you have the moles of unsaturated groups by 1,000 moles of carbons. Melting resistance:
    [0106] [0106] Melt resistance measurements were performed on a Gottfert Rheotens 71.97 (Göettfert Inc .; Rock Hill, SC) connected to a 2000 Gottfert Rheotester capillary rheometer. The fused sample (about 25 to 30 grams) was fed with a 2000 Göettfert Rheotester capillary rheometer, equipped with a flat entry angle (180 degrees) with a length of 30 mm, diameter of 2.0 mm, and a proportion of aspect (length / diameter) of 15. After equilibrating the sample at 190 ° C for 10 minutes, the piston was run at a constant piston speed of 0.265 mm / second. The standard test temperature was 190 ° C. the sample was drawn uniaxially in an acceleration nips setting, located 100 mm below the mold, with an acceleration and 2.4 mm / s2. The tension force was recorded as a function of the speed taken from the “nips” rollers. The melt strength was recorded as the Plateau force (cN) before the ribbon broke. The following conditions were used to measure melt resistance: piston speed = 0.265 mm / second; wheel acceleration = 2.4 mm / s2; capillary diameter - 2.0 mm; capillary length = 30 mm; and barrel diameter = 12 mm. Dynamic mechanical spectroscopy (DMS)
    [0107] [0107] The resins were molded by compression in circular plates of "3 mm thick x 1 inch" at 350 ° F, for five minutes, under 1500 psi of pressure, in air. The sample was then removed from the press, and placed on the counter to cool.
    [0108] [0108] A temperature frequency scan was performed using a TA Instrument "Advanced Rheometric Expansion System" (ARES), equipped with parallel plates of 25 mm (diameter), under a nitrogen purge. The sample was placed on a plate, and allowed to melt for five minutes at 190 ° C. The plates were closed at a mm interval, the sample cut (extra sample that extended beyond the “25 mm diameter” circumference of the plate was removed), and then the test was started. The method had an additional, five-minute delay built-in, to allow the temperature to equilibrate. The experiments were carried out at 190 ° C, over a frequency range of 0.1 to 100 rad / s. The voltage amplitude was constant at 10%. The complex viscosity ƞ *, tan (δ) or delta-tan, viscosity at 0.1 rad / s (V0.1), viscosity at 100 rad / s (V100), and the ratio and viscosity (V0.1 / V100) were calculated from these data. Triple detector gel permeation chromatography (TDGPC) - conventional GPC, GPC light diffusion, gPC and gpcBR viscometry:
    [0109] [0109] For the GPC techniques used here (conventional GPC, GPC light diffusion, GPC viscometry and gpcBR), a triple gel permeation chromatography detector system (3D-GPC or TDGPC) was used. This system consists of a robotic assistant release (RAD), a high temperature GPC system {another high temperature instrument suitable for the GPC includes water (Milford, Mass) model 150C High temperature chromatograph; Polymer Laboratory (Shrophire, UK) Model 210 and Model2 20; and Polymer Char GPCIR (Valencia, Spain), equipped with a precision detector (Amberts, Mass), model 2040 laser light diffusion detector with 2-angles, in an IR4 infrared detector from the Polymer Chair (Valencia, Spain) and a viscometer of the 4-capillary solution (DP (Another suitable viscometer includes Viscotek (Houston, Texas) 150R - viscometer of the 4-capillary solution (DP))).
    [0110] [0110] A GPC with the latter, two independent detectors, and at least one of the previous detectors is sometimes referred to as a “3D-GPC” or “TDGPC”, while the term “GPC” alone generally refers to conventional GPC. Data collection is performed using Polymer Char GPC-IR software (Valencia, Spain). The system is also equipped with an in-line solvent degassing device, obtained from Polymer Laboratories (Shropshire, United Kingdom).
    [0111] [0111] The eluent from the GPC column adjusts the flow through each detector arranged in series, in the following order: LS detector, IR4 detector, then DP detector. The systematic approach to the determination of multiple compensation detectors is carried out 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 Polymer, Chapter 13, (1992)). The results of the triple detector log (MW and intrinsic viscosity) were optimized using a wide polyethylene standard, as outlined in the “Light Scattering (LS) GPC” section below, in the paragraph of equation (5).
    [0112] [0112] The appropriate high temperature of the GPC columns were used, such as four, 30 cm, 12 micron long Shodex HT803 columns, or four, 30 cm, 13 micron “Polymer Labs columns” a mixed pore size package ( Olexis LS, Polymer Labs). Here, the Olexis LS column was used. The sample carousel compartment is operated at 140 ° C, and the column compartment is operated at 150 ° c. The samples are prepared in a concentration and "0.1 gram of polymer in 50 milliliters of solvent". The chromatography solvent and sample preparation solvent is 1,2,4-trichlorobenzene (TCB) containing 200 ppm 2,6-di-tert-butyl4-methylphenol (BHT). The solvent is sparged with nitrogen. The polymeric samples are gently stirred at 160 ° C for four hours. The injection volume is 200 microliters. The flow rate through GPC is adjusted to 1 ml / minute. Conventional GPC
    [0113] [0113] For conventional GPC, the IR4 detector is used, and the adjusted GPC column is calibrated by running 21 polystyrene standards with limited molecular weight distribution. The molecular weight (MW) of the standard ranges from 580 g / mol to 8,400,000 g / mol, and the standards are contained in six "cocktail" mixes. Each standard mixture has at least a dozen separation between the individual molecular weights. Standard blends are purchased from Polymer Laboratories. Polystyrene standards are prepared in “0.025 g in 50 ml of solvent”, for molecular weights equal to, or greater than, 1,000,000 g / mol, and in “0.05 g in 50 ml of solvent” for molecular weights less than 1,000,000 g / mol. The polystyrene standard is dissolved at 80 ° C, with gentle agitation, for 30 minutes. The reduced standard mixtures are run first, and in order to decrease the “highest molecular weight component” to minimize degradation. The peak molecular weights of the polystyrene standard are converted to the molecular weight of polyethylene using Equation (1) (as described in Williams and Ward, “J. Polym. Sci., Polym. Letters”, 6 621 (1968)): Mpolethylene = A x (Polystyrene) B (Eq. 1)
    [0114] [0114] Where M is the molecular weight, polyethylene or polystyrene (as marked), and B is equal to 1.0. It is known by those skilled in the art that it can be in the range of about 0.38 to about 0.44, and is determined in the calibration period, using a wide polyethylene standard, as designated in the section “Light Dispersion (LS ) ”(“ Light Scattering (LS) GPC ”), below in the paragraph of equation (5). Using this polyethylene calibration method to obtain molecular weight values, such as the molecular weight distribution (MWD or Mw / Mn), and related statistics, is defined here as the modified Williams and Ward method. The average number of molecular weight, the average weight of molecular weight, and the molecular weight of z-average are calculated from the following equations:
    [0115] [0115] For the LS-GPC, the precision detector PDI2040 model 2040 is used. Depending on the sample, both the 15 ° angle and the 90 ° angle of the light scattering detector are used for the purpose of calculation. Here, the 15 ° angle was used.
    [0116] [0116] 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 Ligth Scattering from Polymer Solutions ”, Elsevier, Oxford, NY (1987)). The total injected concentration used in determining the molecular weight is obtained from the mass detector area, and the mass detector constant obtained from an appropriate linear polyethylene homopolymer, or one of the weight weight average polyethylene standards known molecular. The calculated molecular weights are obtained using a light scattering constant derived from one or more of the polyethylene standards, mentioned below, and a refractory index concentration coefficient, dn / dc, of 0.104. Generally, the response of the mass detector and the light scattering constant should be determined from a linear pattern with a molecular weight in excess of about 50,000 g / mol. Viscometer calibration can be followed using the method described by the manufacturer, or alternatively, using published values of appropriate linear standards, such as standard reference material (SEM) 1475 a (available from the National Institute of Standards and Technology ( NIST)). Chromatographic concentrations are assumed to be low enough to eliminate the targeting of the second effect of the viral coefficient (concentration of effects on molecular weight).
    [0117] [0117] With 3D-GPC, the absolute weight of the average molecular weight (“Mw, Abs”) is determined using equation (5), below, using the “peak area” method for greater accuracy and accuracy. The “peak area” and the “concentration area” are generated by the combination and chromatography / detectors.
    [0118] [0118] For each LS and DP viscometry profile (for example, see Figures 1, 2, and 3), the x-axis (log MWcc-CPC), where cc refers to the conventional calibration curve is determined as Next. First, the polystyrene standard (see above) is used to calibrate the retention volume within the “MWPS log”. Then, equation 1 (Mpolyethylene - A x (Mpolystyrene) B) is used to convert “log MWPS” to “log MWPE”. The “MWPE log” scale serves as the x-axis for the LS profile of the experimental section (MWPE log is equated for the MW log (cc-CPC). The y-axis for each LS or DP profile is the LS or response of the DP detector normalized by the mass of the injected sample In Figures 1, 2, and 3, the y-axis for each DP profile of the viscometer is the response of the DP detector normalized by the injected sample mass. Initially, the molecular weight and the intrinsic viscosity for a standard sample of linear polyethylene, such as SRM1475a or an equivalent, are determined using conventional calibration (“cc”) for both the molecular weight and the intrinsic viscosity as a function of the elution volume. GpcBR branching index by the triple GPC detector (3D-GPC)
    [0119] [0119] The gpcBR branching index is determined by the first calibration of light scattering, viscosity, and concentration detectors as previously described. The baselines are then subtracted from the scattered light, viscometer, and concentrated chromatograms. The integration window is then adjusted to ensure the integration of the entire low molecular weight retention volume range into the light scattering and chromatograms viscometer that indicates the presence of polymer detectable from the refractory index chromatograms. The linear polyethylene standard is then used to establish the Mark-Houwink constant of polyethylene and polystyrene. During obtaining the constants. During obtaining the constants, the two values are used to construct two conventional linear reference calibrations for polyethylene molecular weight and intrinsic polyethylene viscosity as a function of the elution volume, as shown in Equations (6) and (7):
    [0120] [0120] The gpcBR branching index is a robust method for the characterization of long chain branches as described in Yau, Wallace W., “Examples of Use of 3D-GPC-TREF for polyolefin characterization”, Macromol. Symp. 2007, 257, 29-45. The index avoids the "portion-by-portion" calculations of 3D-GPC traditionally used in determining g 'values and calculating the branching frequency, in favor of all areas of the polymer detector. From the 3D-GPC data, one can obtain the absolute mass weight of the sample of average molecular weight (Mw, Abs) through the light scattering detector (LS), using the peak area method. The method avoids the "portion-by-portion" ratio of the light scattering detector signal to the concentration detector signal, as required in a traditional g 'determination.
    [0121] [0121] With 3D-GPC, the sample's intrinsic viscosity is also obtained regardless of the use of Equation (8). The calculation of the area in equation (5) and (8) offers more precision, because the total sample area is much less sensitive to variation caused by the noise of the detector and 3D-GPC adjusted over the baseline and integration limit. . Most importantly, the calculation of the peak area is not affected by the compensation of the detector volume. Similarly, the high precision, intrinsic viscosity of the sample (IV) is obtained by the area method shown in Equation (8):
    [0122] [0122] Where DPi remains for the differential pressure signal monitored directly from the inline viscometer.
    [0123] [0123] To determine the gpcBR branching index, the light scattering elution area for the sample polymer is used to determine the molecular weight of the sample. The elution area of the viscosity detector for the polymer sample is used to determine the intrinsic viscosity (IV or [ƞ]) of the sample.
    [0124] [0124] Initially, the molecular weight and intrinsic viscosity for a standard linear polyethylene sample, such as SRM1475a or an equivalent, are determined using conventional calibration (“cc”) for both, the molecular weight and the intrinsic viscosity as a depending on the elution volume, by equations (2) and (9):
    [0125] [0125] Equation (10) is used to determine the gpcBR branching index:
    [0126] [0126] Where [ƞ] is the measured intrinsic viscosity, (ƞ] cc is the intrinsic viscosity of conventional calibration, Mw is the average weight of the molecular weight, and Mwcc is the average weight of the molecular weight of the conventional calibration. of molecular weight through light dispersion (LS) using equation (5) is commonly referred to as an “absolute weight average of molecular weight” or “Mw, Abs.” The Mwcc of equation (2) using the calibration curve of conventional GPC molecular weight ("conventional calibration") is often referred to as "main chain molecular weight of the polymer chain", "conventional average molecular weight weight", and "Mw, GPC".
    [0127] [0127] All statistical values with the superscript “cc” are determined using their respective elution volumes, the corresponding conventional calibration as previously described, and the calibration (Ci). Unsubscribed values are values measured based on the mass detector, LALLS, and areas of the viscometer. The KPE value is adjusted iteratively, until the linear reference sample has a gpcBR measured value of zero. For example, the final values for α and Log K for the determination of gpcBR in this particular case are 0.725 and - 3.355, respectively, for polyethylene, and 0.722 and -3.993, respectively, for polystyrene.
    [0128] [0128] Once the K and α values were determined using the procedure discussed previously, the procedure is repeated using the branched samples. Branched samples are analyzed using the final Mark-Houwink constants as the best calibration value “cc”, and equations (2) - (9) are applied.
    [0129] [0129] The interpretation of gpcBR is immediately followed. For linear polymers, the gpcBR calculated from equation (8) will be close to zero, since the values measured by LS and viscometry will be close to the conventional calibration standard. For branched polymers, gpcBR will be greater than zero, especially with high levels of long chain branches, due to the measured molecular weight of the polymer it will be greater than the calculated Mw, cc, and the calculated IVcc will be greater than that of the measured polymer IV . In fact, the gpcBR value represents the fractional IV changes due to the effect of molecular size contraction as a result of polymeric branching. A gpcBR value of 0.5 or 2.0 would mean an effect of the IV molecular size contraction at the level of 50% and 200% respectively, versus a linear polymeric molecular weight of equivalent weight.
    [0130] [0130] For these particular examples, the advantage of using gpcBr, compared to a traditional “g index” and branching frequency calculation, is due to the higher precision of gpcBR. All parameters used in the determination of the gpcBR index are obtained with good precision, and are not adversely affected by the response of the 3D-GPC detector at high molecular weights of the concentration detector. The errors in the alignment of the detector volume also do not affect the accuracy of the gpcBr index determination. Representative calculation of the LS “LSP” profile - Inventive and Comparative:
    [0131] [0131] A GPC elution profile of the normalized-concentrated LS detector response is shown in figures 1 and 2, for inventive Examples 1 and 2, and figures 3 for comparative examples 1, respectively. The quantity that affects the “LSP” value is defined with the help of these figures. The x-axis in the project is the logarithmic value of the molecular weight (MW) by the conventional GPC calculation, or cc-GPC MW. The y-axis is the response of the LS detector normalized to equal concentration of the sample, as measured by the peak area of the concentration detector (not shown). The specific characteristics of the LS elution profile are captured in a window defined by two log-MW limits shown in figures 1 and 2. The lower limit corresponds to an M1 value of 200,000 g / mol, and the upper limit corresponds to an M2 value. 1,200,000 g / mol.
    [0132] [0132] The vertical lines of these two MW limits cross with the LS elution curve at two points. A line segment is drawn connecting these two points of intersection. The height of the LS signal at the first intersection (log M1) results in the quantity S1. The height of the LS signal at the second intersection (log M2) results in the quantity S2. The area under the LS elution curve within two limits Mw results in the amount of area B. The comparison of the LS curve with the line segment connecting the two intersections may be part of the segregated area that is above the line segment (see A2 in figures 2, defined as a negative value) or below the line segment (such as A1 in figures, defined as a positive value). The sum of A1 and A2 results in the amount of area A, the total area of A. This total area A can be calculated as the difference between area B and the area below the line segment. The validity of this approach can be provided by the following two equations (note that A2 is negative as shown in figures 1 and 2). Once (area below the line segment) = (area B) + A2 + A1 = (area B) + (Area A), therefore (Area A) = (Area B) - (Area below the line segment) .
    [0133] [0133] The steps for calculating the “LSP” quantity are illustrated with three examples (inventive example 1 and 2, and Comparative example 1) shown in Table 1 and Table 2:
    [0134] [0134] Step 1, “Slope F” calculation in table 1, using the following two equations: Value_Slope = [(LS2-LS1) / LS2] / dLogM (Eq. 11) SlopeF = a function of the slope = Abs (slope_value - 0.42) + 0.001 (Eq. 12)
    [0135] [0135] Step 2, calculation “AreaF” and “LSF” in table 2, using the following two equations: AreaF = a function of area = Abs (Abs (A / B + 0.033) -0.005) (Eq. 13) where, A / B = (Area A) / (Area B) LSP = Log (area F * slope) + 4 (Eq. 14) Table 1 Calculation of “SlopeF”
    [0136] [0136] Differential scanning calorimetry (DSC) can be used to measure the melting and crystallization behavior of a polymer over a wide temperature range. For example, the TA Instruments Q1000 DSC, equipped with an RCS (refrigerated cooling system) and an auto-sampler is used to perform this analysis. During the test, a flow of nitrogen purifying gas of 50 ml / minute is used. Each sample is pressed by melting in a thin film at about 175 ° C, the molten sample is then cooled in air, at room temperature (-25 ° C). The film sample was formed by pressing a “0.01 to 0.2 gram” sample at 175 ° C at 1,500 psi and 30 seconds to form a “0.1 to 0.2 thousandth thickness” film . A specimen with a diameter of 3-10 mg, six mm is extracted from the cooled, weighed polymer, placed in a light aluminum pan (ca 50 mg), and closed folded (“crimped shut”). The analysis was then carried out to determine its thermal property.
    [0137] [0137] The thermal behavior of the sample was determined by losing control of the sample temperature to create a heat flow versus the temperature profile. First, the sample is quickly heated to 180 ° C and left isothermal for 5 minutes, in order to remove its thermal history. Then, the sample is cooled to -40 ° C, at a cooling rate of 10 ° C / minute, and left isothermal at -40 ° C for five minutes. The sample was then heated to 150 ° C (ie the second “heating” slope) at a heating rate of 10 ° C / minute. The cooling and the second heating curve are recorded. The cooling curve is analyzed by adjusting the baseline of the extreme points from the start of crystallization at -20 ° C. The heating curve is analyzed by adjusting the extreme points of the baseline of -20 ° C until the end of the fusion. The values determined are the peak melting temperature (Tm), peak crystallization temperature (Tc), heat of melting (Hf) (in Joules per gram), and the calculated% crystallinity for the polyethylene samples using:% crystallinity = (Hf) / (292J / g)) x 100 (Eq. 15).
    [0138] [0138] The melting heat and the melting peak temperature are recorded from the second heat curve. The peak crystallization temperature is determined from the cooling curve. Film test:
    [0139] [0139] The following physical properties were measured on the films as described in the experimental section.
    [0140] [0140] Total turbidity (complete) and internal turbidity: internal turbidity and total turbidity were measured according to ASTM D 1003-07. The internal turbidity was obtained via a combined refractive index using mineral oil (1-2 teaspoons), which was applied as a coating on each surface of the film. A Hazegard Plus device (BYK_Gardner, USA; Columbia, MD) was used for the test. For each test, five samples were examined, and an average reported. The sample dimensions were “6 inches x 6 inches”.
    [0141] [0141] 45 ° Brightness: ASTM D2457-08 (average of five film samples, each “10 inch x 10 inch” sample).
    [0142] [0142] Clarity: ASTEM D1746-09 (average of five film samples, each “10 inch x 10 inch” sample).
    [0143] [0143] 2% secant module-MD (machine direction) and CD (transverse direction): ASTMD882-10 (average of five film samples in each direction, each sample “1 inch x 6 inches”).
    [0144] [0144] Elmendorf MD and CD shear strength: ASTM D882-10 (average of five film samples in each direction, each “1 inch x 6 inch” sample).
    [0145] [0145] Dart impact resistance: ASTM D1709-09 (minimum 20 godas to achieve a 50% failure; typically ten “10 inch x 36 inch” strips).
    [0146] [0146] Breaking strength: breaking was measured on an INSTRON 4201 model with software version 3.10 - SINTECH TESTWORKS. The size of the specimen was “6 inches x 6 inches”, and four measurements were taken to determine an average burst value. The film was conditioned for 40 hours after film production, and at least 24 hours in a controlled ASTM laboratory (23 ° C and 50% relative humidity). A “100 pound” load cell was used with a round specimen held 4 inches in diameter. The rupture probe was a polished "½ inch diameter" stainless steel ball (on a 2.5 "rod) with a" maximum travel length of 7.5 inches ".
    [0147] [0147] There is no length gauge, and the probe was as closed as possible, but it did not touch the specimen. The probe was adjusted by increasing the probe until it touched the specimen. Then the probe was gradually decreased, until it did not touch the specimen. Then, a 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, the crosshead distance traveled, and the peak load were used to determine the rupture by the software. The rupture probe was cleaned using a “KIM-WIPE” after each species.
    [0148] [0148] Contraction stress: the contraction stress was measured according to the method described in Y. Jin, T. HermelDavidock, T. Karjala, M. Demirors, J. Wang. E. Leyva, and D. Allen, “Shrink Force Measurement of Low Shrink Force Films,” SPE ANTEC Proceedings, p. 1264 (2008). The shrinkage stress of the film sample was measured by decreasing the test temperature that was conducted on an RSA-III Dynamic Mechanical analyzer (TA Instruments; New Castle, DE) with an ornamental film. The “12.7 mm wide” and “63.5 mm long” film specimens were molded from the film sample, both in the machine direction (MD) and in the transverse direction (CD), for testing . The film thickness was measured using a Mitutoyo absolute digital indicator (Model C112CEXB). This indicator had a maximum measurement 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 width of the specimen, were used to calculate the cross-sectional area of the film (A), in which “A = width x thickness” of the film specimen that was used in the film shrinkage test.
    [0149] [0149] A standard TA Instruments ornamental film tension was used for the measurement. The RSA-III oven was equilibrated at 25 ° C, for at least 30 minutes, before zeroing the gap and axial force. The initial range was adjusted to 20 mm. The film specimen was then attached to both the upper and lower ornament. Typically, measurements for MD only require a measurement of the film thickness. Because the contraction stress in the CD direction is typically less, two or four measurements of the film thickness are stacked together for each measurement to improve the signal-to-noise ratio. In each case, the thickness of the film is the sum of all thickness measurements. In this work, a single measure was used in the MD direction and two measures were used in the CD direction. After the film reached the initial temperature of 25 ° C, the top ornament was manually raised or slightly decreased to obtain an axial force of -1.0g. This will ensure that no excessive warping or stretching of the film occurs at the start of the test. Then the test was started. A constant trim interval was maintained during the total measurement.
    [0150] [0150] The temperature change started at a rate of 90 ° C / minute, from 25 ° C to 80 ° C, followed by a rate of 20 ° C / minute, from 80 ° C to 160 ° C. During the change from 80 ° C to 160 ° C, as the film contracts, the contraction force, measured by the force transducer, was recorded as a temperature function for further analysis. The difference between the “peak force” and the “baseline value before the start of the peak contraction force” is considered to be the shrinkage force (F) of the film. The film's shrinkage stress is the ratio of the shrinkage force (F) to the initial cross-sectional area (A) of the film. Experiments:
    [0151] [0151] Preparation of the ethylene-based polymers of the invention:
    [0152] [0152] Figure 4 is a block diagram of the reaction process system used to produce the examples. The reaction system of the process in figure 4 is partially closed in a loop, double recycling, high pressure, low density polyethylene production system. The process reaction system is comprised of a fresh ethylene supply line 1, an amplifier / primary compressor “BP”, a hypercompressor “Hiper”, and a tube with three zones. The tube reactor consists of a first reaction feed zone, a first line of peroxide initiator 3 connected to a first source of peroxide initiator 11, a second line of peroxide initiator 4 connected to a second source of peroxide initiator 12 ; and a third line of peroxide initiator 5 connected to a third source of peroxide initiator 13. The cooling jackets (using high pressure water) are mounted around the outer casing of the tube reactor and preheated. The tube reactor also consists of a high pressure separator “HPS”, a high pressure recycling line 7, a low pressure separator “LPS”, a low pressure recycling line 9, and a chain transfer agent. (CTA) of the feeding system 13.
    [0153] [0153] The tube reactor additionally comprises three reaction zones demarcated through the peroxide injection point site. The first feed of the reaction zone is connected to the front of the tube reactor, and feeds a portion of the process fluid within the first reaction zone. The first reaction zone starts at injection point # 1 (3), and ends the injection at point # 2 (4). The first peroxide initiator is connected to the tube reactor at injection point # 1 (3). The second reaction zone starts at the injection point # 2 (4). The second reaction zone ends the injection at point # 3 (5). The third reaction zone starts at the injection point # 3 (5). For all examples, 100 percent of the ethylene and recycling ethylene is directed to the first reaction zone, through the first supply conduit in reaction zone 1. This is referred to for the entire front part of the tubular gas reactor.
    [0154] [0154] For Inventive Example 1 and Comparative Example 1, a mixture containing t-butyl-peroxy-2-ethylhexanoate (TBPO), di-t-butyl peroxide (DTBP), tert-butylperoxypivalate (PIV), and a isoparaffinic hydrocarbon solvent (evolution range 171-191 ° C; for example, ISOPAR H) is used as the initiator mixture for the first injection point. For injection points # 2 and # 3, a mixture containing only DTBP, TBPO, and the iso-paraffinic hydrocarbon solvent are used. The conditions of the tube reactor process are given in tables 3, 4 and 5.
    [0155] [0155] Propylene was used as the CTA. Propylene was injected into the ethylene stream in a discharge drum in the first stage of the amplifier. The concentration of the CTA feed to the process was adjusted to control the melt index of the product.
    [0156] [0156] For the inventive Examples 1 and 4, it was found that these pressures and temperatures produced a resin with fractional melting index of LDPE with a wide molecular weight distribution (MWD). Table 5 showed that the reactor pressure was decreased and the peak temperatures of the reactor were raised for the Examples of the invention when compared to the Comparative Example. This was done to maximize the product's molecular weight distribution. The molecular weight of the examples was also maximized by reducing the concentration of the recycling CTA (propylene) fed to the reactor. These process conditions, together with other described process conditions, result in resins with the properties of the invention described here.
    [0157] [0157] The properties of inventive LDPEs and comparative LDPEs are listed in tables 6-11. Table 6 contains the melt index (I2), density, melt strength, and the breaking speed of the melt strength data. The inventive polymers have good melt resistance, but not as high as some of the comparative examples, and provide a good balance of bubble stability in the combination with low gel in the final film, which is often formed from a combination of an LDPE with other material such as LDPE. If the melt strength is too high, there is a very high propensity for gel formation, and also the resin when used in film applications may not be able to be dragged down (“drawn down”) to thin densities.
    [0158] [0158] Table 6 also contains data from the conventional TDGPC, illustrated for the inventive examples with relatively wide molecular weight distribution or MWD or cc-GPC Mw / Mn, and relatively high molecular weight of mean-z, Mz or cc- GPC Mz. Table 7 contains the TDGPC-related properties derived from LS and viscosity detectors, together with the concentration detector, showing that the examples of the invention have an intermediate Mw-abs, Mw (LS-abs) / Mw (cc-GPC ), and gpcBR, and a low LSP, reflective of the relatively wide molecular weight distribution, coupled with a relatively high level of long chain branches, as reflected by a high gpcBR. This design is optimized to result in optimum melt resistance, in order to achieve a good balance of physical properties, along with good dragging ability, bubble stability, productivity, and processability, when forming films or coatings with an LDPE inventive step or combinations with this LDPE.
    [0159] [0159] Table 8 contains the DMS viscosity data, as summarized by the viscosity measurement at 0.1; 1; 10, and 100 rad / s, the viscosity ratio or the viscosity ratio and measurement at 0.1 rad / s for the viscosity measurement at 100 rad / s, all being measured at 190 ° C, and the delta-tan measured at 0.1 rad / s. The low frequency viscosity, the viscosity at 0.1 rad / s, is relatively high for the inventive examples when compared to the comparative examples. A high "low frequency viscosity" can be correlated with good melt strength, bubble stability, and film productivity. The viscosity ratio, which reflects the change in viscosity frequently, is high for the inventive examples when compared to the Comparative Examples. This is reflected in the potentially good processability of the inventive Examples when preparing the blowing film. The delta-tan at 0.1 rad / s is relatively low, indicative of greater fusion elasticity, which can also be correlated with good bubble stability to the blowing film.
    [0160] [0160] Table 9 contains the branches for the 1000C as measured by 13C NMR. These LDPE polymers contain amyl, or C5 branches, that are not contained in substantially linear polyethylene, such as AFFINITY polyolefin plastomers, or LLDPEs, such as DOWLEX polyethylene resins, both produced by The Dow Chemical Company. Each comparative and inventive LDPE, shown in Table 9, contains more than, or equal to, 0.5 amyl group (branches) per 1000 carbon atoms (from the inventive examples it contains more than 1 amyl group (branches) per 1000 atoms of carbon).
    [0161] [0161] Table 10 contains results of unsaturation by 1H NMR. Table 11 contains the DSC results of the melting point, Tm, the heat of fusion, the percentage of crystallinity, and the crystallization point, Tc. Table 3 Flow of peroxide initiator in pounds per hour at each injection point used to manufacture Examples 2-5
    [0162] [0163] Blowing films were made, and physical properties measured, with different LDPEs and a LLDPE (LLDPE1 (DOWLEX 2045G)), LLDPE1 has a “melt index 1.0 (MI or I2), and a density of 0.920 g / cc ”. The films were made in 20% by weight and 80% by weight of the respective LDPE, based on the weight of LDPE and LLDPE1.
    [0163] [0164] Each formulation was composed in a MAGUIRE gravimetric mixer. A polymer processing aid in “1.125% by weight of super batch”, based on the total weight of the formulation. The super-batch PPA (Ingenia AC01-01, available from Ingenia Polymers) contained 8% by weight of DYNAMAR FX-5920ª in a polyethylene vehicle. This amount at 900 ppm PPA in the polymer.
    [0164] [0165] LLDPE1 was also used as LLDPE in films made at maximum productivity. All samples were made with 80% by weight DOWLEX 2045G and 20% by weight of LDPE. Blow Film Production
    [0165] [0166] Monolayer blowing films were made on a “8 inch mold” with a polyethylene with a “Davis Standard Barrier II spindle”. External cooling by an air ring and internal bubble cooling was used. The general parameters of the blowing film, used to produce each blowing film, are shown in table 12. The temperatures are the temperatures close to the pellet retainer (Barrel 1), and in the order of increase, when the polymer was extruded through the mold. Table 12 Conditions for the manufacture of blow film for films
    [0166] [0167] Film samples were taken at a controlled rate and at a maximum rate. The controlled rate was 250 pounds / hour, which is equal to the productivity rate of 10.0 pounds / hour / inch of the circumference of the mold. The diameter of the mold used for the maximum productivity screens was in an 8 inch mold, so that the controlled rate, as an example, the conversion between “pound / hour” and “pound / hour / inch” of the circumference of the mold, is shown in equation 16. Similarly, said equation can be used for other rates, such as the maximum rate, by substituting the maximum rate in equation 16 to determine the “pound / hour / inch” of the circumference of the mold. pound / hour / inch of mold circumference = (250 pound / hour) / (8 * π) = 10 (equation 16)
    [0167] [0168] The maximum rate for a given sample was determined by increasing the productivity rate to the point where bubble stability was the limiting factor. The extruder 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 increased shear rate with higher engine speed (rpm, revolutions per minute ). The maximum bubble stability was determined by taking the bubbles at the point where they would not be sealed in the air ring. At this point, the rate was reduced to that of the bubbles resettled in the air ring, and then a sample was taken. The cooling over the bubbles was adjusted by adjusting the air ring and maintained in the bubbles. This was taken as the maximum productivity rate, while maintaining bubble stability.
    [0168] [0169] The drag properties of the film and the extrusion coating are listed in tables 13-14. As seen in table 13, it was found that the inventive Examples have excellent optics of turbidity, brightness, and transparency, compared to the greater melt resistance of the mixture (film # 1) and (film # 5) at the standard rates and the productivity rate maximum. All "combined films of the Example of the invention" have similar toughness in terms of breakage, dart ("dart"), and breakage, compared to mixtures of the comparative examples, at standard rates and maximum rates, which are important when it is desired for maintain toughness while improving productivity. Films # 6 and film # 7 of the inventive examples have improved maximum productivity over film # 8.
    [0169] [0170] As seen in table 14, it was discovered that the inventive examples used in films # 10 and # 11 have excellent optics of turbidity, brightness, and transparency compared to the higher melt resistance rates (film # 9) in the standard productivity. All "combined films of the example of the invention" have similar or improved toughness, in terms of breakage, and breakage, compared to the higher rate of melt strength (film # 9), at the standard rate, which is important when it is desired maintain hardness while improving productivity. In addition, the inventive film # 10 and # 11 has significantly improved (by more than 15%) the dart (“dart”) characteristic when compared to all other combinations of blends. Table 13 Film properties with 80% LLDPE1 / 20% LDPE - # 1-8 films made in 2 mil at a standard rate (std.) Of 250 lb / h and at a maximum rate (max.) (8 ”mold)
    Table 14 Film properties with 20% LLDPE1 / 80% LDPE films # 9 - 13 made in 2 mil at a standard (std.) Rate of 250 lb / h (8 ”mold)
    权利要求:
    Claims (15)
    [0001]
    Composition, characterized by the fact that it comprises an ethylene-based polymer, which is a low density polyethylene (LDPE), obtained through the polymerization of the ethylene free radical, and the LDPE has a GPC light dispersion parameter “LSP ”Less than 1.60; and the polymer having a viscosity ratio (V0.1 / V100, at 190 ° C) greater than 50.
    [0002]
    Composition, according to claim 1, characterized by the fact that LDPE has a gpcBR value of 1.50 to 2.25.
    [0003]
    Composition according to claim 1, characterized by the fact that the polymer has a melting resistance greater than 15cN and less than 25 cN.
    [0004]
    Composition according to claim 1, characterized by the fact that the polymer has a MWD (conv) of 5 to 8.
    [0005]
    Composition according to claim 1, characterized in that the polymer has a melting index (I2) of 0.01 to 1g / 10 min.
    [0006]
    Composition according to claim 1, characterized in that the polymer has a density of 0.910 to 0.940 g / cm3.
    [0007]
    Composition according to claim 1, characterized in that the polymer has a melt resistance of at least 15 cN and less than 21 cN, and a breaking speed greater than 40 mm / s.
    [0008]
    Composition, according to claim 1, characterized by the fact that the polymer has a MWD (conv) greater than 6.
    [0009]
    Composition according to claim 1, characterized by the fact that the polymer is a low density polyethylene (LDPE), obtained through the free radical polymerization of high pressure of ethylene.
    [0010]
    Article, characterized by the fact that it comprises at least one component formed from the composition defined in claim 1.
    [0011]
    Article, according to claim 10, characterized by the fact that the article is a film.
    [0012]
    Article according to claim 10, characterized in that the article is selected from mono- or multilayer films, molded articles, coatings, fibers, or non-woven fabrics or woven fabric.
    [0013]
    Composition according to claim 1, characterized by the fact that the ethylene-based polymer comprises the following characteristics: (a) at least 0.1 amyl group per 1000 total carbon atoms; (b) a melt viscosity ratio (V0.1 / V100, at 190 ° C) greater than or equal to 58; (c) a melt viscosity at 0.1 rad / s, 190 ° C greater than or equal to 40,000 Pa * s; and (d) a gpcBR value of 1.50 to 2.25.
    [0014]
    Article, characterized by the fact that it comprises at least one component formed from the composition defined in claim 13.
    [0015]
    Article according to claim 14, characterized in that the article is selected from mono- or multilayer films, molded articles, coatings, fibers, or non-woven or woven fabrics.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE69211569T2|1991-12-30|1997-01-23|Dow Chemical Co|ETHYLENE INTERPOLYMER POLYMERIZATION|
    US6545088B1|1991-12-30|2003-04-08|Dow Global Technologies Inc.|Metallocene-catalyzed process for the manufacture of EP and EPDM polymers|
    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|
    US5869575A|1995-08-02|1999-02-09|The Dow Chemical Company|Ethylene interpolymerizations|
    WO2006049783A1|2004-11-02|2006-05-11|Dow Global Technologies Inc.|Process for producing low density polyethylene compositions and polymers produced therefrom|
    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|
    KR20110084905A|2008-10-07|2011-07-26|다우 글로벌 테크놀로지스 엘엘씨|High pressure low density polyethylene resins with improved optical properties produced through the use of highly active chain transfer agents|
    US9243087B2|2009-06-11|2016-01-26|Dow Global Technologies Llc|LDPE enabling high output and good optics when blended with other polymers|
    US20110003940A1|2009-07-01|2011-01-06|Dow Global Technologies Inc.|Ethylene-based polymer compositions for use as a blend component in shrinkage film applications|
    EP2464672B1|2009-08-10|2019-11-27|Dow Global Technologies LLC|Ldpe for use as a blend component in shrinkage film applications|
    ES2380568T3|2009-11-10|2012-05-16|Basell Polyolefine Gmbh|High pressure LDPE, for medical applications|
    US8653196B2|2010-01-11|2014-02-18|Dow Global Technologies, Llc|Method for preparing polyethylene with high melt strength|
    EP2621963B1|2010-09-30|2016-07-06|Dow Global Technologies LLC|Polymerization process to make low density polyethylene|
    CN103347907B|2010-12-17|2016-10-26|陶氏环球技术有限责任公司|Polymer based on ethylene and preparation method thereof|
    IN2015DN02921A|2012-09-28|2015-09-18|Dow Global Technologies Llc|
    IN2015DN02920A|2012-09-28|2015-09-18|Dow Global Technologies Llc|IN2015DN02921A|2012-09-28|2015-09-18|Dow Global Technologies Llc|
    EP2999742A1|2013-05-22|2016-03-30|Dow Global Technologies LLC|Compositions containing low density ethylene-based polymers with high melt strength and films formed from the same|
    JP6377141B2|2013-05-22|2018-08-22|ダウ グローバル テクノロジーズ エルエルシー|Low density ethylene-based compositions with improved melt strength, yield, and mechanical properties|
    CN105440465B|2014-09-29|2017-11-24|中国石油化工股份有限公司|A kind of rubber-plastic composition and preparation method thereof and film|
    CN107108987A|2014-12-01|2017-08-29|陶氏环球技术有限责任公司|Polymer composition, shrink film and its obtained method|
    MX2017006889A|2014-12-01|2017-09-01|Dow Global Technologies Llc|Shrink films, and methods for making thereof.|
    JP6536280B2|2015-08-18|2019-07-03|キョーラク株式会社|Resin for foam molding, method for producing foam molded article|
    US11123953B2|2015-08-31|2021-09-21|Dow Global Technologies Llc|Multilayer films and methods thereof|
    WO2017040088A1|2015-09-02|2017-03-09|Dow Global Technologies Llc|Flexible crosslinked cable insulation and methods for making flexible crosslinked cable insulation|
    CN108349203A|2015-09-29|2018-07-31|陶氏环球技术有限责任公司|Shrink film and its manufacturing method|
    KR101924198B1|2015-12-23|2018-11-30|주식회사 엘지화학|Low density polyethylene copolymer having superior film processibility and transmittance|
    KR20180114081A|2016-02-23|2018-10-17|다우 글로벌 테크놀로지스 엘엘씨|Ethylene-based polymer and method for producing the same|
    JP6932713B2|2016-03-31|2021-09-08|ダウ グローバル テクノロジーズ エルエルシー|Modified polyethylene resin and method for producing it|
    EP3238938A1|2016-04-29|2017-11-01|Borealis AG|Machine direction oriented films comprising multimodal copolymer of ethylene and at least two alpha-olefin comonomers|
    WO2017201110A1|2016-05-18|2017-11-23|Dow Global Technologies Llc|Ethylene-based polymers and processes to make the same|
    EP3589488B1|2017-02-28|2021-09-01|Dow Global Technologies LLC|Ethylene-based polymers with good processability for use in multilayer films|
    ES2783948T3|2017-03-10|2020-09-21|Dow Global Technologies Llc|Multilayer films and methods of the same|
    CN110392704A|2017-03-21|2019-10-29|陶氏环球技术有限责任公司|With the optical polyvinyls of improvement|
    BR112020000057A2|2017-07-06|2020-07-14|Dow Global Technologies Llc|low-temperature multi-layer shrink films and methods of producing them|
    CA3076592A1|2017-09-27|2019-04-04|Dow Global Technologies Llc|Modified polyethylene compositions and method for making the same|
    CN109323897A|2018-09-27|2019-02-12|安徽滁州德威新材料有限公司|A kind of CABLE MATERIALS 1024 test piece of antioxidant and its assessment experimental method|
    WO2020243487A1|2019-05-31|2020-12-03|Dow Global Technologies Llc|Ziegler-natta catalyzed polyethylene resins and films incorporating same|
    CN113950491A|2019-05-31|2022-01-18|陶氏环球技术有限责任公司|Low density polyethylene with improved processability|
    AR119085A1|2019-06-06|2021-11-24|Dow Global Technologies Llc|MULTILAYER BLOWN FILM|
    WO2021076357A1|2019-10-17|2021-04-22|Dow Global Technologies Llc|Multilayer films and articles comprising multilayer films|
    WO2021206941A1|2020-04-06|2021-10-14|Dow Global Technologies Llc|Enhanced melt strength low-density polyethylene for use in films or blends|
    KR102308309B1|2020-12-30|2021-10-06|대진첨단소재 주식회사|System for predicting physical property of recycled acrylonitrile butadiene styrene and operation method thereof|
    KR102308311B1|2020-12-30|2021-10-06|대진첨단소재 주식회사|System for predicting physical property of material using artificial intelectual and operation method thereof|
    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-12-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-08-04| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2021-01-05| B09A| Decision: intention to grant|
    2021-03-02| B09X| Decision of grant: republication|
    2021-03-23| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 13/03/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201261707342P| true| 2012-09-28|2012-09-28|
    US61/707,342|2012-09-28|
    PCT/US2013/030787|WO2014051682A1|2012-09-28|2013-03-13|Ethylene-based polymers and processes to make the same|
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