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    • 专利摘要:
    tubular low density ethylene-based polymers with improved balance of extractables and melt elasticity. the invention provides an ethylene-based polymer comprising the following properties: a) fraction by weight (w) of molecular weight above 5 * 106 g / mol, w> ab * i2, where a = 0.4% by weight, and b is 0.02% by weight / (dg / min), ew <cb * i2%, where c = 0.9% by weight; and b) g '> d? and * log (i2), where d = 162 pa and e = 52 pa / log (dg / min).
    公开号:BR112016013042B1
    申请号:R112016013042-1
    申请日:2014-11-20
    公开日:2020-12-15
    发明作者:Cornelis F. J. Den Doelder；Otto J. Berbee；Stefan Hinrichs；Teresa P. Karjala
    申请人:Dow Global Technologies Llc；
    IPC主号:
    专利说明:

    BACKGROUND OF THE INVENTION
    [001] Resins for extrusion coating on paper, board, aluminum, etc., are designed with wide molecular weight distribution (MWD) and extractable lows. In the application of extrusion coating, the polymer is processed under high temperature conditions, usually 280 ° C to 350 ° C. Large MWD (which normally requires a significant high molecular weight fraction) is necessary for good processability during coating (neck balance and drawdown), while low extractables are required for low smoke formation during coating, under high temperature conditions , and / or for food contact compliance.
    [002] Broad MWD low density polyethylene (LDPE) is composed of high and low molecular weight polymer molecules, and an average molecular weight will determine the melting index. The extractable fraction increases with an increasing fraction of low molecular weight molecules. molecular weight, and is enhanced by increasing the frequency of short chain branching in low molecular weight molecules. Taking into account this combination of characteristics, there is usually a trade-off between coating performance and extractable level.
    [003] Normally, LDPE resins with wide MWD are prepared in an autoclave reactor or a combination of autoclave and tube reactors. Wide MWD resins can be achieved in autoclave reactor systems promoting long chain branching and through distribution of inherent residence time through which molecules will go through shorter (low molecular weight) or longer (high molecular weight) growth paths.
    [004] WO 2013/083285 teaches, among other things, an LDPE having an Mw / Mn that is greater than 15, a storage module G '(5kPa) that is above 3000, and a vinylidene content that is at least 15/100 k C, compositions and a process for the production of LDPE in a tubular reactor by radical-initiated polymerization where polymerization is carried out by reacting the ethylene monomer under the action of one or more radical initiators, for example, peroxides, in that the amount of initiator radical used is at least three times the amount conventionally used. The storage module G 'in the loss module G ”= 5kPa is shown to be generally larger for the inventive LDPE than the standard tubular LDPE produced with conventional techniques.
    [005] WO 2013/078018 A2 and WO 2013/078224 teach that tubular reactor products, which are suitable for the application of the extrusion coating by having ample MWD, extractable lows and sufficient high fusion strength and G 'rheology, can be prepared without any chemical modification, for example, without the use of crosslinking agents in reactors, separators, extruders, etc.
    [006] The intrinsic disadvantage of a more uniform residence time distribution in the tubular against the autoclave process, which negatively limits the MWD amplitude, is compensated by a careful selection of process conditions, such as the reactor configuration, temperature of peak, reactor inlet pressure, conversion level, fresh ethylene and / or CTA distribution, etc.
    [007] For the resins described in the patents above, it was found that at a given melting index (I2), the melting resistance and G 'rheology can be increased at the expense of extractable level in synthesis of products in greater absolute Mw ( abs) and broader MWD adapting process conditions.
    [008] Schmidt et al (Macromolecular Materials and Engineering, Vol 290, p 4004-414, 2005) describes and models the impact of segmented flow distribution in a tubular reactor and its effect on the formation of an ultra-molecular tail high in MWD. Flow segmentation will always be present to some extent by laminar boundary layers on the wall, even when a highly turbulent flow regime is maintained. Flow segmentation in a tubular reactor can be enhanced by dynamic or static inlay. The conditions necessary to prepare the tubular extrusion coating resins lead to a high molecular weight, branched polymer susceptible to fouling and / or chain interlacing with polymer already adhered to the inner tubular wall. The polymers cited in WO 2013/078018 A2 and WO 2013/078224 were prepared under minimum flow segmentation conditions as demonstrated by the low level of the ultra-high molecular weight tail in the light scattering gel permeation chromatography curve (LS GPC ). However, it has been found that depending on the train configuration and / or operating condition, this ultra-high molecular weight tail can be significantly increased as shown by the absolute GPC data. The presence of this ultra-high molecular weight tail will significantly increase Mw (abs) and expand MWD. However, surprisingly, it was found that this increase in Mw (abs) has less impact on the MS and G 'performance of the material produced, leading to a larger Mw (abs) and wider MWD design for the same MS performance and G '. This broader MWD design at a fixed melt index implies more ultra-high molecular weight, as well as more low molecular weight. This usually leads to a higher level of extractable.
    [009] Thus, there is a need for new ethylene-based polymers with extractable lows, even when the MWD is expanded as is the case with potentialized flow segmentation in a tubular process (as analyzed by LS GPC). These new polymers are suitable for extrusion coating applications, and can be prepared in a tubular process showing an increased tendency for flow segmentation. There is still a need for these polymers that can be prepared without any chemical modification, for example, without the use of crosslinking agents in reactors, separators, extruders, etc., or the use of mixing operations. SUMMARY OF THE INVENTION
    [0010] The invention provides a polymer based on ethylene comprising the following properties: a) fraction by weight (w) of molecular weight above 5 * 106 g / mol, w> AB * I2, where A = 0.4% in weight, and B is 0.02% by weight / (dg / min), ew <CB * I2%, where C = 0.9% by weight; and b) G ’> D - E * log (I2), where D = 162 Pa and E = 52 Pa / log (dg / min). BRIEF DESCRIPTION OF THE DRAWINGS
    [0011] Figure 1 shows a polymerization flow scheme containing a tubular reactor.
    [0012] Figure 2 shows GPC (LS) profiles for inventive and comparative polymers.
    [0013] Figure 3 shows the weight fraction (w) of molecular weight above 5 * 106 g / mol against melt index (I2) for inventive and comparative polymers.
    [0014] Figure 4 shows the G '(in G ”= 500 Pa, 170 ° C) against melting index (I2) for inventive and comparative polymers.
    [0015] Figure 5 shows the extractables n-hexane against melt index (I2) for inventive and comparative polymers. DETAILED DESCRIPTION OF THE PREFERENTIAL MODE
    [0016] As discussed above, the invention provides an ethylene-based polymer comprising the following properties: a) fraction by weight (w) of molecular weight above 5 * 106 g / mol, w> AB * I2, where A = 0 , 4% by weight, and B is 0.02% by weight / (dg / min), ew <CB * I2%, where C = 0.9% by weight; and b) G ’> D - E * log (I2), where D = 162 Pa and E = 52 Pa / log (dg / min).
    [0017] The ethylene-based polymer can comprise a combination of two or more modalities as described here.
    [0018] In one embodiment, the ethylene-based polymer has a melting index (I2) of 0.4 to 16 dg / min, or 0.5 to 16 dg / min.
    [0019] In one embodiment, the ethylene-based polymer is selected from a polyethylene homopolymer or an ethylene-based interpolymer.
    [0020] In one embodiment, the ethylene-based polymer is selected from a polyethylene homopolymer or from an ethylene-based copolymer; and wherein the comonomer of the ethylene-based copolymer is selected from vinyl acetate, an alkyl acrylate, carbon monoxide (CO), acrylic acid, a comonomer containing carboxylic acid, or a mono-olefin. In another embodiment, the comonomer is present in an amount of 0.5 to 10% by weight of the comonomer, based on the weight of the copolymer.
    [0021] In one embodiment, the ethylene-based polymer comprises less than 30 mole parts per million (ppm) of a cross-linking agent (capable of forming a covalent bond or bond between two polymer molecules) or a comonomer capable of crosslinking (capable of forming a covalent bond or bond between two polymer molecules), based on the total moles of monomer units in the ethylene-based polymer. In another embodiment, the ethylene-based polymer comprises less than 30 ppm of a comonomer containing several unsaturations or containing an acetylenic functionality.
    [0022] It is understood that trace amounts of impurities can be incorporated into the polymer structure; for example, traces of acetylenic components (less than 20 ppm of mol in polymer) may be present in the ethylene feed according to typical specifications for ethylene (for example, acetylene at a maximum of 5 mol ppm in the supply of ethylene).
    [0023] Desirably, the inventive ethylene-based polymer has low gels. Thus, the direct addition of cross-linking agents or comonomers with cross-linking capability is not desired in the polymerizations of the inventive ethylene-based polymers described herein.
    [0024] In one embodiment, the ethylene-based polymer has an extractable level of n-hexane less than or equal to (<) 4.0% by weight, or 3.5% by weight, or 3.0% by weight , or 2.6% by weight or 2.0% by weight.
    [0025] In one embodiment, the ethylene-based polymer has an extractable level ratio of n-hexane vs melting index: extractable n-hexane <A + B * log (I2), where A = 3.00% by weight and B = 1.66% by weight / log (dg / min).
    [0026] In one embodiment, the ethylene-based polymer has an extractable level ratio of n-hexane vs melting index: extractable n-hexane <A + B * log (I2), where A = 2.30% by weight and B = 1.66% by weight / log (dg / min). The extractable hexane is determined by the standard test method described here.
    [0027] In one embodiment, the extractable n-hexanes from the ethylene-based polymer are <X% by weight + Y * log (I2), where X = 2.3% by weight and Y = 1.66% by weight / log (dg / min).
    [0028] In one embodiment, the extractable n-hexanes from the ethylene-based polymer are <X% by weight + Y * log (I2), where X = 2.3% by weight and Y = 1.66% by weight / log (dg / min) when I2 is as follows: 0.5 dg / min <I2 <12 dg / min, or 0.6 dg / min <I2 <12 dg / min, or 0.8 dg / min <I2 <12 dg / min,
    [0029] In one embodiment, the ethylene-based polymer has a molecular weight fraction (w) above 5 * 106 g / mol, greater than 0.4% by weight and less than 0.7% by weight.
    [0030] In one embodiment, the ethylene-based polymer is a polyethylene homopolymer.
    [0031] In one embodiment, the ethylene-based polymer is an ethylene-based copolymer; and wherein the comonomer of the ethylene-based copolymer is selected from vinyl acetate, an alkyl acrylate, CO, acrylic acid, a comonomer containing carboxylic acid, or a mono-olefin. In another embodiment, the comonomer is selected from vinyl acetate, an alkyl acrylate, acrylic acid, or a monoolefin.
    [0032] In one embodiment, the ethylene-based polymer has a ratio of Mw (abs) against melting index (I2): Mw (abs) <A + B * log (I2), where A = 3, 50 * 105 grams per mole (g / mole), and B = -1.20 * 105 (g / mole) / log (dg / min).
    [0033] In one embodiment, the ethylene-based polymer has an Mw (abs) <250,000 g / mole.
    [0034] In one embodiment, the ethylene-based polymer has an Mw (abs)> G + H * log (I2), where G = 1, 80 * 105 g / mole, or G = 2.00 * 105 g / mole, and H = -1.20 * 105 (g / mole) / log (dg / min).
    [0035] In one embodiment, the ethylene-based polymer has an Mw (abs)> 140,000 g / mole.
    [0036] In one embodiment, the ethylene-based polymer has an Mw (abs) / Mn (abs) of 10.0 to 30.0, or of 15.0 to 25.0, or of 17.0 to 24, 0.
    [0037] In one embodiment, the ethylene-based polymer has a G 'to I2 relationship: G'> D - E * log (I2), where D = 167 Pa and E = 52 Pa / log (dg / min).
    [0038] In one embodiment, the ethylene-based polymer has an I2> 0.5 dg / min, or> 0.8 dg / min, or <20 dg / min, or <16 dg / min, or <dg 12 / min, or <10 dg / min.
    [0039] In one embodiment, the ethylene-based polymer has a density of 0.910 to 0.940 g / cc (1 cc = 1 cm3).
    [0040] In one embodiment, the ethylene-based polymer has a density greater than, or equal to, 0.9160 g / cc, or greater than, or equal to, 0.9180 g / cc.
    [0041] In one embodiment, the ethylene-based polymer has a density less than, or equal to, 0.9250 g / cc, or less than, or equal to, 0.920 g / cc.
    [0042] In one embodiment, the ethylene-based polymer is prepared in a reactor configuration comprising at least one tubular reactor.
    [0043] In one embodiment, the ethylene-based polymer is prepared in a reactor configuration comprising at least one tubular reactor with at least three reactor zones.
    [0044] In one embodiment, the ethylene-based polymer is prepared in a reactor configuration comprising at least one tubular reactor with at least four reactor zones.
    [0045] An inventive ethylene-based polymer can comprise a combination of two or more embodiments as described here.
    [0046] The invention also provides a composition comprising an inventive ethylene-based polymer, as described herein.
    [0047] In one embodiment, the composition further comprises another polymer based on ethylene. In one embodiment of the other ethylene-based polymer there is a polyethylene or LDPE homopolymer.
    [0048] An inventive composition can comprise a combination of two or more modalities as described here.
    [0049] The invention also provides an article comprising at least one component formed from an inventive composition.
    [0050] In one embodiment, the article is an extrusion coating. In another embodiment, the article is a film.
    [0051] An inventive article may comprise a combination of two or more modalities described here. Polymerizations
    [0052] For a polymerization process initiated by free radical, high pressure, two basic types of reactors are known. The first type is a stirred autoclave bottle having one or more reaction zones (the autoclave reactor). The second type is a jacketed tube that has one or more reaction zones (the tubular reactor).
    [0053] The pressure in each autoclave and tubular reactor zone of the process is normally from 100 to 400 megapascals (MPa), more usually from 120 to 360 MPa, and even more usually from 150 to 320 MPa.
    [0054] The polymerization temperature in each tubular reactor zone of the process is normally from 100 to 400 ° C, more usually from 130 to 360 ° C, and even more usually from 140 to 340 ° C.
    [0055] The polymerization temperature in each autoclave reactor zone of the process is normally 150 to 300 ° C, more usually 160 to 290 ° C, and even more usually 170 to 280 ° C. An expert in the art understands that the temperatures in the autoclave are considerably lower and less differentiated than those of the tubular reactor, and thus, more favorable extractable levels are normally observed in polymers produced in autoclave-based reactor systems.
    [0056] The high pressure process of the present invention to produce polyethylene homo or interpolymers having the advantageous properties as found in accordance with the invention, is preferably carried out in a tubular reactor having at least three reaction zones. Initiators
    [0057] The process of the present invention is a free radical polymerization process. The type of free radical initiator to be used in the present process is not critical, but preferably one of the applied initiators must allow high temperature operation in the range of 300 ° C to 350 ° C. Free radical initiators that are commonly used include organic peroxides, such as peresters, percetals, peroxide ketones, percarbonates and cyclic multifunctional peroxides.
    [0058] These organic peroxide initiators are used in conventional amounts, usually from 0.005 to 0.2% by weight, based on the weight of the polymerizable monomers. Peroxides are usually injected as solutions diluted in a suitable solvent, for example, in a hydrocarbon solvent.
    [0059] Other suitable initiators include azodicarboxylic esters, azodicarboxylic dinitriles and 1,1,2,2-tetramethylethane derivatives, and other components capable of forming free radicals in the desired operating temperature range.
    [0060] In one embodiment, an initiator is added to at least one polymerization reaction zone, and in which the initiator has a half-life temperature in a second greater than 255 ° C, preferably greater than 260 ° C. in another embodiment, these initiators are used at a peak polymerization temperature of 320 ° C to 350 ° C. In another embodiment, the initiator comprises at least one peroxide group incorporated in a ring structure.
    [0061] Examples of such initiators include, but are not limited to, TRIGONOX 301 (3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonaan) and TRIGONOX 311 (3,3,5,7, 7-pentamethyl-1,2,4-trioxepano), both available from Akzo Nobel, and HMCH-4-AL (3,3,6,6,9,9-hexamethyl-1,2,4,5-tetroxonane) available from United Initiators. See also WO 02/14379 and WO 01/68723. Chain Transfer Agents (CTA)
    [0062] Chain transfer agents or telogens are used to control the melt index (MI or I2) in a polymerization process. Chain transfer involves terminating the growth of polymer chains, thus limiting the last molecular weight of the polymer material. Chain transfer agents are usually hydrogen atom donors that will react with a growing polymer chain, stop the polymerization reaction of the chain, and start the growth of a new polymer molecule. These agents can be of many different types and include saturated hydrocarbons or unsaturated hydrocarbons, aldehydes, ketones and alcohols. By controlling the concentration of the selected chain transfer agent, one can control the length of the polymer chains, and therefore the molecular weight, for example, the numerical average molecular weight, Mn. The melt index of a polymer, which is related to Mn, is controlled in the same way.
    The chain transfer agents used in the process of this invention include, but are not limited to, aliphatic hydrocarbons, such as, for example, pentane, hexane, cyclohexane, propene, pentene or hexane; ketones such as acetone, diethyl ketone or diamyl ketone; aldehydes such as formaldehyde or acetaldehyde; and saturated aliphatic alcohols such as methanol, ethanol, propanol or butanol.
    [0064] An additional way of influencing the melting index includes the accumulation and control, in ethylene recycling streams, of incoming ethylene impurities such as methane and ethane, peroxide dissociation products such as tertbutanol, acetone, etc. , and or solvent components used to dilute the initiators. These ethylene impurities, peroxide dissociation products and / or dilution solvent components can act as chain transfer agents.
    [0065] The distribution of the chain transfer agent along and in the reaction zones is an important parameter to expand the molecular weight distribution (MWD) and increase the melting resistance, keeping all other process conditions constant. See International Publication No. WO2013 / 059042 for descriptions of how to use fresh ethylene and / or CTA feed distribution to influence the distribution of chain transfer agent throughout and in reaction zones. Polymers
    [0066] In one embodiment, the ethylene-based polymers of this invention have a density of 0.914 to 0.940, more normally 0.916 to 0.930 and even more normally 0.918 to 0.926, grams per cubic centimeter (g / cc or g / cm3) . In one embodiment, the ethylene-based polymers of this invention have a melt index (I2) of 0.3 to 16, or 0.4 to 16, or 0.5 to 16, or 0.8 to 14, or 0.8 to 12 grams per 10 minutes (g / 10 min) at 190 ° C / 2.16 kg.
    [0067] Ethylene-based polymers include LDPE homopolymer, and high pressure copolymers, including ethylene / vinyl acetate (EVA), ethylene ethyl acrylate (EEA), ethylene butyl acrylate (EBA), ethylene acrylic acid (EAA), and ethylene carbon monoxide (ECO). Other suitable comonomers are described in Ehrlich, P .; Mortimer, G.A .; Adv. Polymer Science; Fundamentals of Free-radical Polymerization of Ethylene; Vol. 7, pp.386-448 (1970). In one embodiment, comonomers exclude comonomers capable of crosslinking polymer chains, for example, containing various unsaturations or an acetylenic functionality. Monomer and Comonomers
    [0068] The term ethylene interpolymer as used in the present description and in the claims, refers to ethylene polymers and one or more comonomers. Comonomers suitable for use in the ethylene polymers of the present invention include, but are not limited to, ethylenically unsaturated monomers and especially C3-20 alpha-olefins, carbon monoxide, vinyl acetate, and C2-6 alkyl acrylates. In one embodiment, ethylene-based polymer does not contain comonomers capable of crosslinking polymer chains, for example, comonomers containing various unsaturations or containing acetylenic functionality. Mixtures
    [0069] The inventive polymers can be mixed with another or more other polymers, such as, among others, linear low density polyethylene (LLDPE); copolymers of ethylene with one or more alpha-olefins, such as, among others, propylene, butene-1, pentene-1, 4-methyl-pentene-1, pentene-1, hexene-1 and octene-1; high density polyethylene (HDPE) such as HDPE grades HD 940-970 available from The Dow Chemical Company. The amount of inventive polymer in the mixture can vary widely, but it is usually 10 to 90, or 15 to 85, or 20 to 80 weight percent (% by weight), based on the weight of the polymers in the mixture. LDPE (inventive) / LLDPE mixtures usually provide good optical and processing characteristics, and / or are useful in the preparation of laminations, and / or are useful in such applications as films, extrusion coatings, foams, and wires and cables.
    [0070] In one embodiment, the invention is a composition comprising a mixture of an ethylene-based polymer of this invention and an ethylene-based polymer of this invention, for example, an LDPE that differs from the ethylene-based polymers of this invention in one or more properties such as extractable n-hexane, or (w) fraction of molecular weight above 5 * 106 g / mol, w> AB * I2, where A = 0.4% by weight, and B is 0.02 % by weight / (dg / min), ew <CB * I2%, where C = 0.9% by weight, etc. Additions
    [0071] One or more additives can be added to a composition comprising an inventive polymer. Suitable additives include stabilizers; fillers, such as organic or inorganic particles, including clays, talc, titanium dioxide, zeolites, powdered metals, organic or inorganic fibers, including carbon fibers, silicon nitride fibers, steel wire or mesh, and nylon cord or polyester, nanomeric particles, clays and so on; thickeners, and oil extenders, including paraffinic or naphthenic oils. applications
    [0072] An inventive composition can be employed in a variety of conventional thermoplastic manufacturing processes to produce useful articles, including extrusion coatings; movies; and shaped articles, such as blow-molded, injection-molded, or rotational molded articles; foams; yarn and cable, fibers, and woven or non-woven fabrics. DEFINITIONS
    [0073] Unless otherwise stated, implicit in context, or customary in the technique, all parts and percentages are based on weight, and all testing methods are current as of the filing date of that disclosure.
    [0074] The term "composition", as used here, refers to a mixture of materials comprising the composition, as well as reaction products and decomposition products formed from the materials of the composition.
    [0075] The terms "mixture" or "polymer mixture", as used, mean an intimate physical mixture (that is, without reaction) of two or more polymers. A mixture may or may not be miscible (from a non-separated phase at the molecular level). A mixture may or may not contain one or more domain configurations, as determined from transmission electron spectroscopy, light scattering, X-ray scattering, and any other method known in the art. The mixing can be done by physically mixing the two or more polymers at the macro level (for example, melt or composition mix resins) or the micro level (for example, simultaneous formation within the same reactor).
    [0076] The term "polymer" refers to a compound prepared by the polymerization of monomers, of the same or different type. The generic term polymer, therefore, includes the term homopolymer (which refers to polymers prepared from only one type of monomer with the understanding that trace amounts of impurities can be incorporated into the polymer structure), and the term "interpolymer" as defined below. Trace amounts of impurities can be incorporated into and / or within the polymer.
    [0077] The term "interpolymer" refers to polymers prepared by the polymerization of at least two different types of monomers. The generic term interpolymer includes copolymers (which refer to polymers prepared from two different monomers), and polymers prepared from more than two different types of monomers.
    [0078] The term "ethylene-based polymer" or "ethylene polymer" refers to a polymer that comprises a majority amount of polymerized ethylene, based on the weight of the polymer and, optionally, can comprise at least one comonomer.
    [0079] The term "ethylene-based interpolymer" or "ethylene interpolymer" refers to an interpolymer that comprises a majority amount of polymerized ethylene, based on the weight of the interpolymer, and comprises at least one comonomer.
    [0080] The term "ethylene-based copolymer" or "ethylene copolymer" refers to an interpolymer comprising a majority amount of polymerized ethylene, based on the weight of the copolymer, and only one comonomer (thus, only two types monomer).
    [0081] The term "reaction zone" refers to a flask, for example, a reactor, or a section of a flask, in which the polymerization reaction is initiated by the addition of radicals or components that dissociate into, and / or generate radicals. Exemplary flasks or reactors include, among others, autoclaves, tubular reactors, extruder reactors, etc. The reaction medium can be heated and / or cooled by a heat transfer medium flowing through the jacket around the reaction zone.
    [0082] The term “first reaction zone,” as used here, refers to the reactor zone where polymerization is first initiated by the addition of radicals or components that dissociate into, and / or generate, radicals. The first reaction zone ends at the point where there is a new supply of fresh and / or recycled ethylene and / or radicals and / or components that dissociate into, and / or generate, radicals.
    [0083] The terms "subsequent reaction zone", or "sequential reaction zone", as used here, refer to a reactor zone that receives ethylene and polymer from a previous reactor zone, and where the radicals or components , which dissociate into, and / or generate, radicals, are added to the entrance to the subsequent (or sequential) reactor zone. The subsequent (or sequential) reaction zone ends at the point where there is a new supply of fresh and / or recycled ethylene and / or radicals and / or components that dissociate into, and / or generate, radicals; however, the umpteenth reaction zone ends at the position of a pressure control device in the reactor system. The number of subsequent (or sequential) reaction zones is (n- 1), where n is the total number of reaction zones. The second reaction zone is the subsequent or sequential reaction zone of the first reaction zone, and so on.
    [0084] The terms "comprising", "including", "having" and their derivatives are not intended to exclude the presence of any additional component, step or procedure, regardless of whether it is specifically disclosed. For the avoidance of doubt, all compositions claimed through the use of the term "comprising" may include any additive, adjuvant or additional compound, polymeric or not, unless otherwise indicated. In contrast, the term, “which essentially consists of” excludes from the scope any recitation succeeding any other component, step or procedure, except those that are not essential for operability. The term “consisting of” excludes any component, step or procedure not specifically outlined or listed. TEST METHODS
    [0085] Density: The samples for the density measurement were prepared according to ASTM D 1928. Polymer samples are pressed at 190 ° C and 30,000 psi for three minutes, and then at 21 ° C and 207 MPa for one minute. Measurements were prepared within one hour of sample pressing using ASTM D792, Method B.
    [0086] Melting index: Melting index, or I2, (g / 10 min or dg / min) is measured according to ASTM D 1238, Condition 190 ° C / 2.16 kg. I10 is measured with ASTM D 1238, Condition 190 ° C / 10 kg. Gel Permeation Light Scattering Chromatography (GPC-LS):
    [0087] Triple Detector Gel Permeation Chromatography (TD-GPC): The high temperature TD-GPC analysis is performed on an ALLIANCE GPCV2000 (Waters Corp.) set at 145 ° C. The flow rate for the GPC is 1 milliliter per minute (mL / min). The injection volume is 218.5 microliters (μ L). The column set consists of four, Mixed-A columns (20 micron (μm) particles; 7.5 X300 mm; PolymerLaboratories Ltd).
    [0088] Detection is obtained by means of an IR4 detector from PolymerChAR, equipped with a CH sensor; a Wyatt Technology Dawn DSP Multi-angle Light Scattering (MALS) detector (Wyatt Technology Corp., Santa Barbara, CA, USA), equipped with a 30 megawatt argon ion laser (mW) operating at À = 4 88 nm; and a Waters three capillary viscosity detector. The MALS detector is calibrated by measuring the spreading intensity of the 1,2,4-trichlorobenzene (TCB) solvent. The normalization of photodiodes is prepared by injecting SRM 1483, a high density polyethylene (HDPE) with an average molecular weight (Mw) of 32,100 and polydispersity (molecular weight distribution) of 1.11. An increment of specific refractive index (dn / dc) of 0.104 mL / mg, for polyethylene and, TCB, is used.
    [0089] Conventional GPC calibration is done with narrow polystyrene 20 (PS) standards (Polymer Laboratories Ltd.) with molecular weights in the range of 580-7,500,000 g / mol. The standard peak molecular weights of polystyrene are converted to molecular weights of polyethylene using the following equation: Mpolethylene = A * (Mpolystyrene), with A = 0.39, and B = 1. The value of A is determined using a homopolymer of linear high density polyethylene (HDPE) with 115,000 g / mol Mw. This HDPE reference material is also used to calibrate the IR detector and viscometer, assuming 100% mass recovery and an intrinsic viscosity of 1,873 dL / g.
    [0090] Distilled TCB grade “Baker Analyzed” (JT Baker, Deventer, The Netherlands), containing 200 ppm 2,6-di-tert-butyl-4-methylphenol (Merck, Hohenbrunn, Germany), is used as a solvent for sample preparation, as well as for the 3Det-GPC experiment. HDPE SRM 1483 is obtained from the U.S. National Institute of Standards and Technology (Gaithersburg, MD, USA).
    [0091] LDPE solutions are prepared by dissolving the samples, under gentle agitation, for three hours at 160 ° C. PS standards are dissolved in the same conditions for 30 minutes. The sample concentration is 1.5 mg / ml, and the polystyrene concentrations are 0.2 mg / ml.
    [0092] A MALS detector measures the scattered signal of polymers or particles in a sample under different scattering angles θ. The basic light scattering equation (from M. Anderson, B. Wittgren, K.-G. Wahlund, Anal. Chem. 75, 4279 (2003)) can be written as follows:
    where Rθ (is the excess Rayleigh ratio, K is an optical constant, which is, among other things, dependent on the increment of the specific refractive index (dn / dc), c is the concentration of the solute, M is the molecular mass, Rg is the radius of rotation, and X is the wavelength of the incident light. Calculating the molecular weight and radius of rotation from the light scattering data requires extrapolation to the zero angle (see also PJ Wyatt, Anal. Chim Minutes 272, 1 (1993)) This is done by plotting (Kc / Rθ) ^ as a function of sin2 (θ / 2) in the so-called Debye graph. The molecular weight can be calculated from the intercept with the ordinate, and the radius of rotation from the initial slope of the curve The second virial coefficient is considered insignificant The intrinsic viscosity numbers are calculated from the viscosity and concentration detector signals taking the ratio of the specific viscosity and the concentration in each slice of elution.
    [0093] The ASTRA 4.72 software (Wyatt Technology Corp.) is used to collect the signals from the IR detector, the viscometer, and the MALS detector, and perform the calculations.
    [0094] Molecular weights calculated, for example, the average molecular weight in absolute weight Mw (abs), and absolute molecular weight distributions (for example, Mw (abs) / Mn (abs)) are obtained using a spreading constant of light derived from one or more of the aforementioned polyethylene standards and a refractive index concentration coefficient, dn / dc, of 0.104. Generally, the response of the mass detector and the light scattering constant should be determined from a linear pattern with an excess molecular weight of about 50,000 Daltons. Viscometer calibration can be 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 were assumed to be low enough to eliminate addressing the effects of the 2nd viral coefficient (effects of concentration in molecular weight).
    [0095] The MWD (abs) curve obtained from TD-GPC is summarized with three characteristic parameters: the average molecular weight of absolute weight Mw (abs), the absolute numerical average molecular weight Mn (abs), ew, where w is defined as “fraction weight of molecular weight greater than 5 x 106 g / mole, based on the total polymer weight, and as determined by GPC (abs)”.
    [0096] In the form of an equation, the parameters are determined as follows. The numerical integration of the “logM” and “dw / dlogM” table is usually done with the trapezoidal rule:

    [0097] The sample used in the measurement of G 'is prepared from a compression molding plate. A piece of aluminum foil is placed on a backing plate, and a model or mold is placed on top of the backing plate. Approximately 12 grams of resin is placed in the mold, and a second piece of aluminum foil is placed over the resin and mold. A second backing plate is then placed on top of the aluminum foil. The total set is placed in a compression molding press, which is performed under the following conditions: 3 min at 150 ° C, at a pressure of 10 bar, followed by 1 min at 150 ° C, at 150 bar, followed by cooling of “1.5 min” break at room temperature, at 150 bar. A 25 mm disc is stamped outside the compression molded plate. The thickness of the disc is approximately 2.0 mm.
    [0098] The measurement of rheology to determine G ’is made in a nitrogen environment, at 170 ° C, and a voltage of 10%. The stamped disc is placed between the two parallel “25 mm” plates located in an ARES-1 rheometer oven (Rheometrics SC), which is preheated, for at least 30 minutes, to 170 ° C, and the gap of the “25 mm” parallel plates are slowly reduced to 1.65 mm. The sample is then allowed to stay for exactly 5 minutes in these conditions. The oven is then opened, the excess sample is carefully cut around the edge of the plates, and the oven is closed. The storage module and the sample loss module are measured using a small amplitude, oscillatory shear, according to a descending frequency scan of 100 to 0.1 rad / s (when it is able to obtain a value of G ” less than 500 Pa at 0.1 rad / s), or from 100 to 0.01 rad / s. For each frequency scan, 10 points (logarithmically spaced) per decade of frequency are used.
    [0099] The data are plotted (G '(Y axis) against G ”(X axis)) on a log-log scale. The Y axis scale covers the range from 10 to 1000 Pa, while the X axis scale covers the range of 100 to 1000 PA. The Orchestrator software is used to select data in the region where G ”is between 200 and 800 Pa (or using at least 4 data points). The data are fitted to a polynomial log model using the adjustment equation Y = C1 + C2 ln (x). Using Orchestrator software, G ’to G” equal to 500 Pa is determined by interpolation. Standard Method for Extractable Hexane
    [00100] Polymer pellets (from polymerization, pelletizing process without further modification, approximately 2.2 grams of pellets pressed into a film) are pressed in Carver Press, in a thickness of 3.0 - 4.0 mils. The pellets are pressed at 190 ° C, for three minutes, at 3,000 lbf, and then at 190 ° C, for three minutes, at 40,000 lbf. Gloves without residue (PIP * CleanTeam * Cotton Lisle Inspection Gloves, Part Number: 97-501) are used, so as not to contaminate films with residual oils from the operator's hands. Films are cut into "1 inch x 1 inch" squares, and weighed. Sufficient film samples are used, so that 2.5 g of film samples are used for each extraction. The films are then extracted for two hours, in a hexane flask containing about 1000 ml of hexane, at “49.5 ± 0.5 ° C” in a heated water bath.
    [00101] The hexane used is an isomeric mixture of hexanes (eg Hexanes (Optima), Fisher Chemical, high purity mobile phase for HPLC and / or extraction solvent for GC applications, 99.9% min per GC) . After two hours, the films are removed, washed in clean hexane, initially dried with nitrogen and then still dried in a vacuum oven (80 ± 5 ° C) in full vacuum (ISOTEMP Vacuum Oven, Model 281A at approximately 30 inches Hg ) for two hours. The films are then placed in a desiccator, and cooled to room temperature for a minimum period of one hour. The films are then re-weighed, and the amount of mass loss due to hexane extraction is calculated. EXPERIMENTAL Comparative Example (A, B and C) Reaction Scheme
    [00102] Comparative examples A, B, C were manufactured using the flow diagram of a high pressure polymerization plant shown in Figure 1. The flow (1) is the composition of fresh ethylene, which is compressed together with the outlet of the reinforcement compressor (Reinforcement) by two primary compressors (Primary A and Primary B) for flow (2) and flow respectively 3. Flow (2) is combined with the high pressure recycling flow (18) and distributed over the flow (4) and flow (19). The flow (4) is fed to the suction side of the secondary compressor (Hyper), which feeds the compressed ethylene on the flow side (8). Flow 3 is combined with flow (19) and fed to the suction side of the secondary compressor (Hyper), which feeds compressed ethylene through flow 9 (Front) to the front of the reactor. The flow (8) is distributed over the lateral feed flows (20) and (21), which are aligned to the entrance of the 2nd and 3rd reaction zones respectively.
    [00103] Flow (6) and (7) shows the feeds of compositions of the chain transfer agent (CTA) system. The secondary compressor (Hyper) pressurizes the ethylene feed streams, containing a chain transfer agent system, at a level sufficient to supply the high pressure tubular reactor (Reactor).
    [00104] The tubular reactor (Reactor) is equipped with three reaction zones. Flow 9 is preheated to a sufficiently high onset temperature before polymerization is initiated in the 1st reaction zone. In the reactor, polymerization is initiated with the help of injected and / or activated free radical initiation systems at the entrance of each reaction zone. The maximum temperature in each reaction zone is controlled at a defined point by regulating the concentration and / or amount of feed from the initiation system at the beginning of each reaction zone. After finishing the reaction, and having applied several cooling steps, the reaction mixture is depressurized and / or cooled in (10), and separated in the high pressure separator (HPS). The high pressure separator separates the reaction mixture in a flow rich in ethylene (15), containing unconverted CTA and small amounts of waxes and / or entrained polymer, and a flow rich in polymer (11), which is sent for separation additional for the low pressure separator (LPS). The ethylene stream (15) is cooled and cleaned in the stream (17). Flow 16 is a purge flow to remove impurities and / or inert materials.
    [00105] The polymer separated in LPS is further processed in (12). The ethylene removed in the LPS is fed to the reinforcement compressor (Reinforcement), where during compression, condensables, such as solvent, lubricating oil and other components, are collected and removed through the flow (14). The output of the booster compressor is combined with the composition ethylene flow (1), and further compressed by the primary compressors. Reaction Protocol
    [00106] Polymerization was carried out in the tubular reactor with three reaction zones. In each reaction zone, pressurized water was used for cooling and / or heating the reaction medium, by circulating this water through the reactor jacket. The inlet pressure was 2100 bar, with the pressure drop over the entire tubular reactor system being about 300 bars. Each reaction zone had an inlet and an outlet.Each inlet flow consisted of the outflow from the previous reaction zone and / or an ethylene-rich feed stream added. Ethylene was supplied according to a specification, which allowed a small amount (maximum of 5 ppm mol) of acetylene in ethylene. Thus, the maximum, potential amount of acetylene incorporated in the polymer is less than, or equal to, 16 mole ppm, based on the total moles of monomer units in the ethylene-based polymer (see conversion level in Table 3). Unconverted ethylene and other gaseous components at the reactor outlet were recycled through high pressure and low pressure recycles, and were compressed and distributed through the reinforcement, the primary and hyper (secondary) compressors, according to the flow diagram shown. in Figure 1 (reference numbers in the following paragraphs refer to the various elements in Figure 1). Organic peroxides (see Table 1) were fed to each reaction zone.
    [00107] Acetone was used as a chain transfer agent, and was present at each entrance of the reaction zone originating from the low pressure and high pressure recycling flows (# 13 and # 15), as well as from the composition of CTA recently injected flow # 7 and / or flow # 6. In this comparative example, the weight ratio between the "CTA composition" flows # 7 and # 6 was 3.6 (for A), 3.6 (for B) and 3.3 (for C) respectively.
    [00108] After reaching the first peak temperature (maximum temperature) in reaction zone 1, the reaction medium was cooled with the help of pressurized water. At the exit of reaction zone 1, the reaction medium was further cooled by injecting a feed stream rich in fresh, cold, ethylene (# 20), and the reaction was restarted, feeding an organic peroxide. This process was repeated at the end of the second reaction zone, to allow additional polymerization of the third reaction zone. The polymer was extruded and pelleted (about 30 pellets per gram), using a single screw extruder design at a melting temperature of 230-250 ° C. The weight ratio of feed flows rich in ethylene for the three reaction zones was 1.00: 0.75: 0.25. The values of R2 and R3 were each 2.16 in all examples. R values are calculated in accordance with US Provisional Order No. 61/548996 (International Order No.PCT / US12 / 059469). The internal process speed was approximately 12.5, 9 and 11 m / sec for the 1st, 2nd and 3rd reaction zones, respectively. Additional information can be found in Tables 2 and 3. Table 1: Initiators of Comparative Examples
    Table 2: Pressure and Temperature Conditions of Comparative Examples
    Table 3: Additional Information from Comparative Examples
    Inventive Examples (IE 1, 2, 3)
    [00109] The polymerization was carried out in a tubular reactor with four reaction zones. In each reaction zone, pressurized water was used for cooling and / or heating the reaction medium, by circulating this water in a countercurrent way through the reactor jacket. The inlet pressure was 2150 bar. The ethylene transfer rate was around 45 t / h. Each reaction zone had an inlet and an outlet.Each inlet flow consisted of the outflow from the previous reaction zone and / or an ethylene-rich feed stream added. Ethylene was supplied according to a specification, which allowed a small amount (maximum of 5 ppm mol) of acetylene in ethylene. Thus, the maximum, potential amount of acetylene incorporated in the polymer is less than, or equal to, 16 mole ppm, based on the total moles of monomer units in the ethylene-based polymer. Unconverted ethylene, and other gaseous components at the reactor outlet, were recycled through high pressure and low pressure recycles, and were compressed through a reinforcement, a primary compressor and a hyper (secondary). Organic peroxides (see Table 4) were fed to each reaction zone. For each polymerization, propionaldehyde (PA) and n-butane were used as a chain transfer agent, and were present in each reaction zone. The ethylene-rich reactor feed streams contain homogeneous concentrations of the applied chain transfer agents.
    [00110] After reaching the first peak temperature (maximum temperature) in reaction zone 1, the reaction medium was cooled with the help of pressurized water. At the exit of reaction zone 1, the reaction medium was further cooled by injecting a feed stream rich in fresh, cold ethylene, containing organic peroxide for restarting. At the end of the second reaction zone, to allow additional polymerization of the third reaction zone, organic peroxides were fed. This process was repeated at the end of the third reaction zone to allow additional polymerization of the fourth reaction zone. The polymer was extruded and pelleted (about 30 pellets per gram), using a single screw extruder design at a melting temperature of about 230-250 ° C. The weight ratio of ethylene-rich feed streams for the four reaction zones was X: (1.00-X): 0.00: 0.00, where X is the weight fraction of the ethylene-rich feed stream Overall, X is specified in Table 6, as “Ethylene forward /% by weight”. The speed of the internal process was approximately 15, 13, 12 and 12 m / s for the 1st, 2nd, 3rd and 4th reaction zones, respectively. Additional information can be found in Tables 5 and 6.Table 4: Initiators for Inventive Examples
    Table 5: Pressure and Temperature Conditions of Inventive Examples
    Table 6: Additional Information for Inventive Examples

    [00111] Polymer properties are shown in Tables 7 and 8. Table 7: Inventive and Comparative Polymers
    * Commercial Polymers ** EC: Comparative Example; IE: Inventive Example; AC: Based on autoclave; tub X-Connection: Tubular Reticulation; tub: Tubular. *** Old Dow LDPE 160Ct) Available from The Dow Chemical Company. Table 8: Properties of Polymers in Claims
    w> AB * I2, where A = 0.4% by weight and B is 0.02% by weight / (dg / min); w <CB * I2, where A = 0.9% by weight and B is 0.02% by weight / (dg / min); G '> DE * log (I2), where D = 162 Pa and E = 52 Pa / log (dg / min); an extractable hexane <X + Y * log (I2), where X = 2.3% by weight and Y = 1.66% by weight / log (dg / min)
    [00112] The inventive examples have an excellent balance of polymer properties. Average level of the ultra-high molecular weight tail related to the pre-peak, expressed in w (the weight fraction of the molecules with a molar mass greater than 5 x 106 g / mol); advantageous low extractables, and high elasticity G '.
    [00113] Comparative examples, PG7004 and PT7009, are LDPE autoclave. These examples have extractable lows, but have significantly higher ultra-high molecular weight fraction for the same G 'level, compared to the inventive samples.
    [00114] Comparative example LDPE 160C is a tubular resin that has moderate to high G 'values, is accompanied with high extractables, and has a significantly higher fraction of ultra-high molecular weight compared to the inventive samples. This example is an example of a class of polymers that acquire six G 'of unadapted magnification, which can give high w, but at the same time, many species of low molar mass (Mw (abs) / Mn (abs) that affect negatively extractables (ie leads to more extractables)). Its G ’is also not as high as that achieved in inventive polymers here.
    [00115] Comparative example SABIC NEXCOAT5 (modified with a crosslinking agent) is a tubular resin that has a high G 'value, but is devoid of the pre-peak, and thus has a low w.
    [00116] Comparative examples A to C are tubular resins with high G ’, but without the pre-peak, and having low w. They also have larger extractables in a given I2 than the inventive samples.
    [00117] Figure 2 shows the MWD of three selected resins, PT7009, CE B and IE 1. It is clear that IE 1 has a different high molecular weight tail than both of these comparative products.
    [00118] All properties are considered in relation to the melting index, which is shown in Figures 2-4. The inventive polymers have intermediate w (Figure 3), high G '(Figure 4), and extractable lows (Figure 5) for their MI and Mw and Mw / Mn.
    [00119] The high G 'of the inventive polymers is good for extrusion coating and other strong flow applications, such as blown and molten film and foaming. Broad MWD is required for extrusion coating and related applications. Tubular products are typically narrower in MWD than autoclave products. The tubular LDPE MWD can be expanded by applying coupling and / or branching agents, and / or by optimized process conditions, such as peak temperature, pressure (leading to potentialized LCB levels), and specific CTA application. Within the process condition option, the inventive examples present are a special case where the MWD expansion is further reinforced through induction or the presence of a segmented flow, which leads to the introduction of an ultra-high molecular weight fraction in the polymer This type of magnification is expected to be especially good for lowering the low cup extension flow when compared to samples devoid of that fraction. The extractable lows of the inventive polymers are good for high quality processing, for example, reducing smoke formation in extrusion operations, and relevant for food contact applications.
    [00120] Although the invention has been described in considerable detail in the previous examples, this detail is for the purpose of illustration, and should not be construed as a limitation on the invention as described in the following claims.
    权利要求:
    Claims (13)
    [0001]
    1. Ethylene-based polymer, characterized by the fact that it comprises the following properties: a) fraction by weight (p) of molecular weight above 5 * 106 g / mol, w> AB * I2, where A = 0.4% in weight, and B is 0.02% by weight / (dg / min), ew <CB * I2%, where C = 0.9% by weight; b) G '(in G ”equal to 500 Pa)> D - E * log (I2), where D = 162 Pa and E = 52 Pa / log (dg / min), c) a Mw (abs) / Mn (abs) from 17.0 to 24.0; and d) extractable n-hexanes are <X% by weight + Y * log (I2), where X = 2.3% by weight, and Y = 1.66% by weight / log (dg / min).
    [0002]
    2.Ethylene-based polymer according to claim 1, characterized by the fact that the polymer has a melting index (I2) of 0.3 to 16 dg / min.
    [0003]
    3. Polymer according to either of Claims 1 and 2, characterized in that the polymer has an extractable n-hexane level less than or equal to 3.5% by weight.
    [0004]
    4.Polymer, according to claim 1 or 2, characterized by the fact that the extractable n-hexanes are <X% by weight + Y * log (I2), where X = 2.3% by weight and Y = 1, 66% by weight / log (dg / min) when I2 is as follows: 0.5 dg / min <I2 <12 dg / min.
    [0005]
    5. Polymer according to any one of claims 1 to 4, characterized in that the ethylene-based polymer has a molecular weight fraction (w) above 5 * 106 g / mol, greater than 0.4 % by weight and less than 0.7% by weight.
    [0006]
    6. Polymer according to any one of claims 1 to 5, characterized in that the ethylene-based polymer has a density of 0.916 to 0.925 g / cm3.
    [0007]
    Polymer according to any one of claims 1 to 6, characterized in that the ethylene-based polymer has a melt index (I2) of 0.8 to 10 dg / min.
    [0008]
    Polymer according to any one of claims 1 to 7, characterized in that the ethylene-based polymer is a polyethylene homopolymer.
    [0009]
    9. Polymer according to claim 8, characterized by the fact that the ethylene-based polymer is LDPE.
    [0010]
    Polymer according to any one of claims 1 to 9, characterized in that the ethylene-based polymer is prepared in a reactor configuration comprising at least one tubular reactor.
    [0011]
    11. Polymer according to claim 10, characterized in that the tubular reactor comprises at least three reaction zones.
    [0012]
    12. Composition, characterized by the fact that it comprises the ethylene-based polymer of any one of claims 1 to 11.
    [0013]
    13.Article, characterized by the fact that it comprises at least one component formed from the composition of claim 12.
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    法律状态:
    2020-02-11| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-09-24| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-12-15| 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 20/11/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
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    US201361918275P| true| 2013-12-19|2013-12-19|
    US61/918,275|2013-12-19|
    PCT/US2014/066607|WO2015094566A1|2013-12-19|2014-11-20|Tubular low density ethylene-based polymers with improved balance of extractables and melt elasticity|
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