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    • 专利摘要:
    high pressure polymerization process to form an ethylene based polymer, ethylene based polymer, composition, article and film a high pressure polymerization process to form an ethylene based polymer comprising the steps of: (a) injecting a first feed comprising ethylene and optionally a chain transfer agent (cta system) system into a first autoclave reactor zone operating under polymerization conditions to produce a first zone reaction product, the first cta system reactor zone having a transfer activity z1; and (b) (1) transferring at least part of the first zone reaction product to a second reactor zone selected from a second autoclave reactor zone or tubular reactor zone and operating under polymerization conditions, and optionally ( 2) recently injecting a second feed into the second reactor zone to produce a second zone reaction product, provided that the second reactor zone contains a cta system having a transfer activity z2; and with the proviso that the ratio of z1 / z2 is less than 1.
    公开号:BR112012015026B1
    申请号:R112012015026-0
    申请日:2010-12-14
    公开日:2019-11-05
    发明作者:F J Den Doelder Cornelis；Nijohf Egbert；Demirors Mehmet；J Berbee Otto；A De Vries Sjoerd
    申请人:Dow Global Technologies Llc；
    IPC主号:
    专利说明:

    “HIGH PRESSURE POLYMERIZATION PROCESS TO FORM A POLYMER BASED ON ETHYLENE, POLYMER BASED ON ETHYLENE, COMPOSITION, ARTICLE AND FILM
    Field of the invention [001] This invention relates to polymers based on ethylene, particularly low density polyethylene (LDPE), and polymerization improvements to prepare LDPE. Mainly, the polymerization process involves autoclaves reactors, preferably operated sequentially with tubular reactors.
    History of the invention [002] Currently, there are many types of polyethylene produced and sold. In particular, a type is produced by several suppliers and sold in large quantities. This polyethylene is called high pressure polyethylene via free radicals (usually called LDPE) and usually prepared using a tubular reactor or an autoclave reactor or sometimes a combination. Sometimes, users mix LDPE with other polymers such as linear low density polyethylene (LLDPE) to try to modify properties such as fluidity or processability.
    [003] We have now discovered new LDPE polymers that have improved extrusion coating properties and can have improved shrinkage in combination with rigidity, tensile strength, melt strength and favorable optical properties, while still maintaining other performance attributes.
    [004] For example, S. Goto et al., Journal of Applied Polymer Science: Applied Polymer Symposium, 36, 21-40, 1981 (Ref. No. 1) has the following general discussion regarding
    Petition 870190057554, of 6/21/2019, p. 5/55
    2/45 reaction kinetics. Low density polyethylene resins with higher densities (> 926 kg / m 3 ) are produced at reduced polymerization temperature in order to reduce the frequency of short chain branching and, consequently, increase the product density. Both the rate of short-chain branching reaction (also known as back attack) as well as that of the long-chain branching reaction step (also known as polymer transfer) are highly temperature dependent.
    [005] The table below shows the kinetic data of the reaction steps involved (Ref. N ° 1). The temperature dependence is given by the activation energy. The higher the activation energy, the more a given reaction step will be promoted by a higher temperature or reduced by lower temperatures.
    Elemental reaction rate rate constants (Ref. No. 1) Reaction step Frequency factor Activation energy, cal / mol Activation volume, cm 3 / mol Propagation 5, 63E + 11 10,520 -19, 7 LCB 1.75E + 12 14,080 4.4 SCB 5, 63E + 12 13,030 -23, 5
    [006] For polymeric properties, the ratio between the rate of a given reaction step and the rate of propagation is important.
    [007] Expresses itself The property of dependency in temperature by Δ energy of activation as well for:[008] Frequency in SCB in product: Δ energy in activation = 13.03 - 10, 52 = 2.51 kcal / mol. [009] Frequency in LCB in product: Δ energy in activation = 14.08 - 10, 52 = 3.57 kcal / mol.
    [010] The data above suggests that the frequency of LCB
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    3/45 decreases faster than the frequency of SCB with decreasing temperature. In addition, lower maximum polymerization temperatures required to decrease the frequency of SCB will also decrease the polymer concentration (/ profile) in the reactor. In addition, since the LCB reaction rate also depends on the polymer concentration, the LCB frequency will decrease when the polymer density increases. This means that the frequency of LCB decreases both because of the lower polymerization temperature and the lower polymer concentration in the reactor when the density of LDPE is increased.
    [011] The molecular weight distribution of polyethylene is greatly affected by the frequency of LCB. High LCB frequency leads to wide MWD resins, while low LCB frequency leads to narrow MWD resins. This means that it becomes increasingly difficult and at some point impossible to produce wide MWD polyethylene resins when the polymer density is increased. Wide MWD polyethylene is required in a variety of extrusion applications, specifically to control melt rheology. An example is the need for low narrowing during extrusion coating.
    Summary of the invention [012] The invention provides a high pressure polymerization process to form an ethylene-based polymer, comprising the steps of: (A) Injecting a first feed comprising ethylene and, optionally, a transfer agent system (CTA system) in a first autoclave reactor zone operating under polymerization conditions to produce a
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    4/45 first zone, the transfer activity of the first feed being Z1; and (B) (1) Transfer at least part of the reaction product from the first zone to a second reactor zone selected from a second autoclave reactor zone or a tubular reactor zone and operating under polymerization conditions, and, optionally, ( 2) recently injecting a second feed into the second reactor zone to produce a second zone reaction product, with the proviso that the second reactor zone contains a CTA system having a Z2 transfer activity; and with the proviso that the Z1 / Z2 ratio is less than 1.
    [013] In an embodiment the invention is a propylene-based polymer prepared by the inventive process. In one embodiment the invention is an ethylene-based polymer having a density of 0.926 to 0.935 g / cm3, and a melt index greater than (>) 3 g / 10 min, and a melt elasticity, in centiNewton , greater than or equal to (8.1 x (melt index) -0.98 ). In one embodiment the invention is a composition comprising the inventive ethylene-based polymer. In an embodiment the invention is an article, for example, a film, comprising the inventive composition.
    Brief description of the drawings [014] Figure 1 is a graph of Fused Elasticity Log (ME) versus Melt Index Log (MI) for Comparative Example 1 and Example 2;
    [015] Figure 2 is a graph of brightness and light diffusion for Example 2c and Comparative Example 1b;
    [016] Figure 3 is a graph of stretching (meters per minute (m / min) and narrowing millimeters (mm)) Example 2c and Comparative Example 1b; and
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    5/45 [017] Figure 4 is a graph of brightness and light diffusion for Example 4 and Comparative Example 3.
    Description of embodiments of the invention
    Overview [018] As discussed above, the invention provides a high pressure polymerization process to form an ethylene-based polymer comprising the steps of: (A) Injecting a first feed comprising ethylene and, optionally, an agent system chain transfer (CTA system) in a first autoclave reactor zone operating under polymerization conditions to produce a first zone reaction product, the CTA system of the first reactor zone having a Z1 transfer activity; and (B) (1) Transfer at least part of the reaction product from the first zone to a second reactor zone selected from a second autoclave reactor zone or a tubular reactor zone and operating under polymerization conditions, and, optionally, ( 2) recently injecting a second feed into the second reactor zone to produce a second zone reaction product, with the proviso that the second reactor zone contains a CTA system having a Z2 transfer activity; and with the proviso that the Z1 / Z2 ratio is less than 1.
    [019] In an incorporation, the process further comprises one or more steps of transferring a zone reaction product produced in the (i-th - 1) zone to an i-th reaction zone, where 3 <i <n, en> 3 and each zone operating under polymerization conditions, and optionally adding an ith feed comprising a CTA system in the i-th reaction zone, the CTA system of the i-th reaction zone
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    6/45 having a transfer activity Z1; and with the proviso that the Z1 / Zi <1 ratio for all i <n and Z1 <Zn.
    [020] In an incorporation, in step A of the process the first feed comprises a CTA system having a transfer activity Z1.
    [021] In an incorporation, in step B of the process in which the product of the first reactor zone and / or the recently injected feed comprises a Cta system resulting in the CTA system of the second reactor zone having a transfer activity Z2.
    [022] In an embodiment, a second feed is injected into the second reactor zone, and the second feed comprises ethylene.
    [023] In a merger, a second feed from the previous merger also comprises a CTA system.
    [024] In an embodiment, a second feed is injected into the second reactor zone, and the second feed comprises ethylene, but does not comprise a CTA system.
    [025] In incorporation, the first food in any an of incorporations previous comprises fur one less comonomer. [026] In incorporation, the second food in any an of incorporations previous comprises fur one less comonomer. [027] In incorporation, the i-th food in any an of incorporations previous further comprises ethylene.[028] In incorporation, the i-th food in any an of incorporations previous further comprises
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    7/45 at least one comonomer.
    [029] In one embodiment, at least one comonomer of any of the previous embodiments is injected into one or more of (I) a suction for a hyper-compressor, (II) a hyper-compressor discharge, and (III) one or more zones of tubular reactor or autoclave.
    [030] In an embodiment, the at least one comonomer of any of the previous embodiments is acrylate, silane, vinyl ester, unsaturated carboxylic acid, and carbon monoxide.
    [031] In a incorporation of process in any an of incorporations previous, at phases (B) (1) and (B) (2) are performed simultaneously. [032] In a incorporation of process in any an of incorporations previous, at phases (B) (1) and (B) (2) are performed on different times.[033] In a incorporation of process in any an of incorporations previous, fur any less part and product in
    first zone reaction is transferred to a second autoclave reactor zone.
    [034] In a process incorporation of any of the previous incorporations, the second autoclave reactor zone is adjacent to the first autoclave reactor zone.
    [035] In a process incorporation of any of the previous incorporations, the second autoclave reactor zone is separated from the first autoclave reactor zone by one or more reactor zones.
    [036] In a process incorporation of any of the previous incorporations, at least part of the first zone reaction product is transferred to a tubular reactor.
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    8/45 [037] In a process incorporation of any of the previous incorporations, the tubular reactor zone is adjacent to the first autoclave reactor zone.
    [038] In a process incorporation of any of the previous incorporations, the tubular reactor zone is separated from the first autoclave reactor zone by one or more reactor zones.
    [039] In a process incorporation of any of the previous incorporations, each feed for each reactor zone contains the same CTA system. In an additional embodiment, the CTA system for each feed contains a single CTA.
    [040] In a process incorporation of any of the previous incorporations, at least one of the feeds for at least one of the reactor zones contains a CTA that is different from at least one of the CTAs for the other reactor zones.
    [041] In a process incorporation of any of the previous incorporations, each CTA is, independently, one of an olefin, an aldehyde, a ketone, an alcohol, a saturated hydrocarbon, an ether, a thiol, a phosphine, an amino, an amine, an amide, an ester, and an isocyanate.
    [042] In a process incorporation of any of the previous incorporations, each CTA is, independently, methyl ethyl ketone (MEK), propanal (propionic aldehyde), butene-1, acetone, isopropanol or propylene.
    [043] In a process incorporation of any of the previous incorporations, at least one CTA has a Cs chain transfer constant greater than 0.001.
    [044] In an incorporation of the process of any of the
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    9/45
    incorporations previous, all autoclave zones
    are located in the same autoclave reactor.
    [045] In a incorporation of the process of any of the
    previous incorporations, the autoclave zones are located in two or more different autoclaves reactors.
    [046] In a incorporation of the process of any of the incorporations previous, the autoclave zones are
    approximately the same size.
    [047] In a incorporation of the process of any of the
    Previous incorporations, two or more of the autoclave zones are of different sizes.
    [048] In a process incorporation of any of the previous incorporations, the polymerization conditions in each reactor zone are operated at the same temperature and pressure.
    [049] In a incorporation of the process of any of the incorporations previous, at least one condition of polymerization in at least one reactor zone is different
    other polymerization conditions.
    [050] In a incorporation of the process of any of the incorporations previous, each of the conditions of polymerization in the reactor zones, comprises,
    independently, a temperature greater than or equal to 100 ° C, and a pressure greater than or equal to 100 MPa.
    [051] In a incorporation of the process of any of the incorporations previous, each of the conditions of polymerization in the reactor zones, comprises,
    independently, a temperature less than 400 ° C, and a pressure less than 500 MPa.
    [052] In a incorporation of the process of any of the
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    10/45 previous incorporations, the Z1 / Zi <1 ratio for all i <n and Z1 / Zn is less than 0.95.
    [053] In a process incorporation of any of the previous incorporations, the Z1 / Zi <1 ratio for all i <n and Z1 / Zn is less than 0.90.
    [054] In a process incorporation of any of the previous incorporations, the Z1 / Zi <1 ratio for all i <n and Z1 / Zn is greater than or equal to 0.
    [055] In a process incorporation of any of the previous incorporations, the Z1 / Zi <1 ratio for all i <n and Z1 / Zn is greater than 0.
    [056] In an embodiment, the invention is a process in which the second feed is injected into the second reaction zone, and the second feed comprises a CTA system.
    [057] In an embodiment, the invention is a process in which the second feed is injected into the second reaction zone, and the second feed does not comprise a CTA system.
    [058] In an embodiment, an inventive process may comprise a combination of two or more embodiments described herein.
    [059] In an embodiment, the invention is an ethylene-based polymer prepared by the process according to any of the previous embodiments.
    [060] In an embodiment, the ethylene-based polymer is polyethylene homopolymer.
    [061] In an embodiment, the ethylene-based polymer is an ethylene-based interpolymer.
    [062] In an embodiment, the invention is an ethylene-based polymer having a melt elasticity, in centiNewton, greater than 8.1 x (melt index) -0.98 .
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    11/45 [063] In an embodiment, the invention is an ethylene-based polymer having a melt elasticity, in centiNewton, greater than 9.3 x (melt index) -0.98 .
    [064] In an embodiment, the invention is an ethylene-based polymer having a melt index greater than 3.0 g / 10 min.
    [065] In an embodiment, the invention is an ethylene-based polymer having a melt elasticity, in centiNewton, greater than 8.1 x (melt index) -0.98 and a melt index greater than 3.0 g / 10 min.
    [066] In one embodiment, the invention is an ethylene-based polymer having a density of 0.926 to 0.935 g / cm 3 .
    [067] In an embodiment, the invention is an ethylene-based polymer having a melt elasticity, in centiNewton, greater than 8.1 x (melt index) -0.98 and a density of 0.926 to 0.935 g / cm 3 .
    [068] In an embodiment, the invention is an ethylene-based polymer having a melt elasticity, in centiNewton,
    bigger that 8 , 1 x (melt index) 0.9 8, a melt index bigger that 3 , 0 g / 10 min, and a density of 0.926 to 0, 935 g / cm 3 .[069] In an incorporation, the polymer based of ethylene, in wake up with any of incorporations previous in polymer, is a homopolymer of polyethylene. [070] In an incorporation, the polymer based of ethylene, in wake up with any of incorporations previous in polymer, is an interpolymer to ethylene based .[071] In an incorporation, the polymer based of ethylene, in wake up with any of incorporations previous in polymer, is an LDPE.
    [072] An inventive ethylene-based polymer can
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    12/45 comprise a combination of two or more embodiments described herein.
    [073] In an embodiment, the invention is a composition comprising an ethylene-based polymer as defined by any of the previous polymer embodiments.
    [074] In an embodiment, the composition comprises yet another polymer based on ethylene.
    [075] An inventive composition may comprise a combination of two or more embodiments described herein.
    [076] In an embodiment, the invention is an article comprising at least one component formed from a composition as defined by any of the previous composition embodiments.
    [077] An inventive article may comprise the combination of two or more embodiments described here.
    [078] In an embodiment, the invention is a film comprising at least one layer formed from a composition as defined by any of the previous composition embodiments.
    [079] An inventive film may comprise the combination of two or more embodiments described herein.
    [080] In an embodiment, the invention is a coating comprising at least one layer formed from a composition as defined by any of the previous composition embodiments.
    [081] An inventive coating may comprise the combination of two or more embodiments described herein.
    Polymerizations [082] For a polymerization process initiated by free radicals at high pressure, two types are known
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    Basic 13/45 of reactors. In the first type, a stirred autoclave container is used having one or more reaction zones: the autoclave reactor. In the second type, a jacketed tube is used as a reactor having one or more reaction zones: the tubular reactor. The high pressure process of the present invention to produce polyethylene homopolymers or copolymers having the advantageous properties found in accordance with the invention, can be performed in an autoclave reactor having at least 2 reaction zones or in a combination of an autoclave and a tubular reactor.
    [083] The temperature in each tubular reactor or autoclave zone of the process is typically 100 to 400 ° C, more typically 150 to 350 ° C and even more typically 160 to 320 ° C. When used here “high pressure means that the pressure in each zone of the tubular reactor or autoclave in the process is at least 100 MPa, and typically is from 100 to 400 MPa, more typically from 120 to 360 MPa and even more typically from 150 at 320 MPa. The high pressure values used in the process of the invention have a direct effect on the amount of chain transfer agent, for example, MEK or propanal (propionic aldehyde), incorporated in the polymer. The higher the reaction pressure, the more units of chain transfer agent will be incorporated into the product.
    [084] In an embodiment of the process of the invention, a combination of an autoclave comprising at least two reaction zones and a conventional tubular reactor having at least one reaction zone is used. In an additional incorporation, such a conventional tubular reactor is cooled by an external water jacket and has at least one injection point for
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    14/45 initiator and / or monomer. Appropriate, but not limiting, reactor lengths can be between 500 and 1500 meters. Normally, the autoclave reactor has several injection points for initiator and / or monomer.
    [085] The particular reactor combination used allows conversion rates above 20 percent, which are significantly higher than the conversion rates obtained by standard autoclaves reactors, which allow conversion rates of around 16-18 percent, expressed as ethylene conversion, for the production of low density polymers.
    [086] Examples of suitable reactor systems are described in USP 3,913,698 and 6,407,191.
    Monomers and comonomers [087] The term ethylene copolymer when 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, acetylenic compounds, conjugated and unconjugated dienes, polyenes, unsaturated carboxylic acids, monoxide carbon, vinyl esters, and C2-6 alkyl acrylates. Initiators [088] The process of the present invention is a polymerization process via free radicals. The type of free radical initiator to be used in the present process is not critical. Free radical initiators that are generally used for such processes are oxygen, which is usable in tubular reactors in conventional amounts between 0.0001
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    15/45 and 0.01 weight percent (weight percent) designed for the weight of polymerizable monomer, and organic peroxides. Typical and preferred initiators are organic peroxides such as peresters, percetals, peroxy ketones and percarbonates, ditherciobutyl peroxide, cumila perneodecanoate, and tercioamyl perpivalate. Other suitable initiators include azodicarboxylic esters, azodicarboxylic dinitriles and 1,1,2,2-tetramethyl ethane derivatives. These organic peroxy initiators are used in conventional amounts between 0.005 and 0.2% by weight designed for the weight of polymerizable monomers.
    Chain transfer agents (CTA) [089] Chain transfer agents or telogens are used to control the melt flow rate in a polymerization process. Chain transfer involves terminating the growth of polymeric chains, thus limiting the final molecular weight of the polymeric material. Typically, chain transfer agents are hydrogen atom donors that will react with a growing polymer chain and interrupt the chain polymerization reaction. These agents can be of many different types, from saturated hydrocarbons or unsaturated hydrocarbons to aldehydes, ketones or alcohols. By controlling the concentration of the chain transfer agent, one can control the length of polymeric chains, and, consequently, the molecular weight. In the same way, the melt flow index (MFI or I2) of a polymer that is related to molecular weight is controlled.
    [090] The chain transfer agents used in the process of this invention include, but are not limited to,
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    16/45 aliphatic and olefinic hydrocarbons, such as pentane, hexane, cyclohexane, propene, pentene or hexene; ketones, such as acetone, diethyl ketone or diamyl ketone; aldehydes, such as formaldehyde or ethanal (acetic aldehyde); and saturated aliphatic alcohols, such as methanol, ethanol, propanol or butanol. Preferred chain transfer agents are those with a chain transfer constant (Cs) of at least 0.001 (for example, propane, isobutane), more preferably of at least 0.01 (for example, propylene, isopropanol, acetone, 1-butene), and even more preferably at least 0.05 (for example, methyl ethyl ketone (MEK), propionic aldehyde, terciobutanethiol). Cs are calculated as described by Mortimer at 130 ° C and 1360 atm (atmosphere) (Ref. No. 1-3 in Table A, below). The maximum value of C s does not exceed 25, typically it does not exceed 21.
    [091] In an embodiment, the amount of chain transfer agent used in the process of the present invention is 0.03 to 10.0 weight percent, preferably 0.1 to 2.0 weight percent based on amount of monomer introduced into the reactor system.
    [092] The manner and timing of the introduction of CTA into the process of the invention can vary widely as long as CTA and / or ethylene are recently injected into at least two reaction zones. Typically, the CTA is fed downstream into a reaction zone (2 a and / or 3 a and / or 4 a , etc.) together with ethylene and / or other reaction components, for example, comonomers, initiator, additives, etc. ., and in addition, some CTA can be fed into the first reaction zone. The first reaction zone is an autoclave.
    [093] In an incorporation, CTA of incorporation, that is, CTA
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    17/45 replacement for the CTA consumed in the first reaction zone is fed together with new ethylene through direct injection and / or together with the injected peroxide solution.
    [094] In an incorporation, additional (new) ethylene without CTA is fed as a constitution flow for the ethylene consumed in the first reaction zone than in the first autoclave reaction zone and / or in one or more reaction zones downstream .
    [095] In an incorporation, the constituting CTA is a CTA with a Cs greater than the CTA's Cs fed in the first reaction zone. This can increase the level of conversion in the reactor system.
    [096] In an incorporation, the CTA comprises a monomeric group, such as propylene, butene-1, etc. The monomeric group improves reactor conversion (it increases CTA consumption).
    [097] In an incorporation, the CTA and / or operational conditions are selected in the recycling sections such that the CTA will condense or separate from the resulting recycling ethylene in less CTA recycled back to the reactor inlet.
    [098] In an incorporation, the CTA is purged from the reactor system in a downstream process section.
    [099] In one embodiment, the reactor system comprises two autoclave reaction zones followed by two tubular reaction zones, and ethylene monomer and CTA are fed into both autoclave reaction zones, but not in any tubular reaction zone .
    [100] In an embodiment, the reactor system comprises two autoclave reaction zones followed by two zones
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    18/45 reaction tubes, and ethylene monomer and CTA are fed to both autoclave reaction zones, but not to any tubular reaction zones, but the initiator is fed to one or both of the tubular reaction zones.
    Polymers [101] Wide MWD polyethylene is required for a variety of extrusion applications, specifically to control rheology in the molten state. An example is the need for narrowing during extrusion coating.
    [102] In one aspect, the polymer of this invention has a broader MWD than other polymers prepared in similar reactors that do not use the split CTA concept (Z1 / Zi = 1). This is exemplified and quantified with the melt / melt index elasticity balance, which is a sensitive method for showing these differences as shown by the examples and comparative examples. It is also exemplified by the improvement in extrusion coating performance.
    [103] In one embodiment, polymers based on ethylene of this invention have a typical density of 0, 910-0, 940 g / cm3, more typically from 0.915 to 0.940 g / cm 3, and even more typically from 0.926 to 0.935 g / cm3 (gram per cubic centimeter). In one embodiment, the ethylene-based polymers of this invention have a melt index (I2) of 0.1 to 100 g / 10 min, more typically 0.5 to 50 g / 10 min and even more typically 3.0 at 20 g / 10 min at 190 ° C / 2.16 kg. In one embodiment, the ethylene-based polymers of this invention have a melt elasticity of 1 to 30 cN (centiNewton), typically 1.5 to 15 cN. In an incorporation, the polymers to be
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    The ethylene base of this invention has two or more of these properties of density, melt index and melt elasticity.
    [104] Ethylene-based polymers include LDPE homopolymer (preferred), and high-pressure copolymers include ethylene / vinyl acetate (EVA), ethylene / ethyl acrylate (EEA), ethylene / acrylic acid ( EAA), and LDPE (<0.926 g / cm3).
    Mixtures [105] The inventive polymers can be mixed with one or more other polymers such as, but not limited to, ethylene / butyl acrylate (EBA) and linear. Product applications include interleaving shrink film, label film, expanded and cast film, blow molding, foam, standard mix / composition and injection molding, etc., for both medium density polyethylene (> 0.926 g / cm3 ) as standard density low density polyethylene (LLDPE), ethylene copolymers with one or more alpha-olefins such as, but not limited to, propylene, butene-1, pentene-1,4,4-methyl-1-pentene, hexene-1 and octene-1; high density polyethylene (HDPE) such as grade 940970 HDPE obtainable from The Dow Chemical Company. The amount of inventive polymer in the mixture can vary widely, but it is typically 10 to 90% by weight, 10 to 50% by weight or 10 to 30% by weight based on the weight of the polymers in the mixture. If the inventive polymer has a relatively narrow MWD (for example, below 6) then the inventive polymer will typically make up the majority of the mixture, based on the weight of the polymers in the mixture. If the inventive polymer has a relatively large MWD (for example,
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    20/45 example, greater than or equal to 6) then the inventive polymer will typically constitute the smallest part of the mixture, i.e. it will be low in LDPE, and will contain less than 50% by weight of the inventive polymer, based on the weight of the polymers in the mixture. Mixtures rich in LDPE typically provide good optics, and / or are useful in the preparation of laminations. Typically, mixtures low in LDPE exhibit good processability, and / or are useful in applications such as extrusion coating and film blowing.
    Additives [106] One or more additives can be added in 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 or polyester cord, nanoparticles, and so on; tacking agents, thinning oils, including paraffinic or naphthenic oils. In addition, other natural and synthetic polymers can be added to an inventive composition, including other polymers that are prepared according to the inventive process and polymers prepared by other processes.
    Uses [107] The polymer of this invention can be employed in a variety of conventional thermoplastic fabrication processes to produce useful articles, including objects comprising at least one layer of film, such as one layer film, or at least one layer in one
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    21/45 multilayer film prepared by casting, blowing, calendering, or extrusion coating processes; molded articles, such as blow-molded, injection-molded, or rotational molded articles; extrusions; fibers; foams; and woven and non-woven cloths. Thermoplastic compositions comprising the ethylene polymer include mixtures with other natural or synthetic materials, polymers, additives, reinforcing agents, ignition-resistant additives, antioxidants, stabilizers, colorants, diluents, crosslinkers, blowing agents, and plasticizers.
    [108] The inventive polymer can be used in the production of fibers for other applications. Fibers that can be prepared with the polymer of this invention, or a mixture comprising a polymer of this invention, include cut fibers, tow, multi-component fibers, core / film, twisted and monofilament. Suitable processes for fiber formation include meltblown, rolled material techniques, such as disclosed in USP 4,340,563 (Appel, et al.), 4,663,220 (Wisneski, et al.), 4,668,566 (Nohr, et al. ), and 4,322,027 (Reba), spun gel fibers disclosed in USP 4,413,110 (Kavesh, et al.), woven and non-woven fabrics disclosed in USP 3,485,706 (May), or structures made from such fibers , including mixtures with other fibers, such as polyester, nylon or cotton, thermoformed articles, extruded shapes, including extrusions and co-extrusions of profiles, calendered articles, and stretched, twisted, or crimped fibers or yarns.
    [109] The inventive polymer can be used in a variety of films including, but not limited to,
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    22/45 extrusion coating coated with various substrates, brightness shrink films, interleaving shrink films, stretched hollow films, silage films, stretched protective cover, sealants, and diaper liners. The inventive polymer is also useful in other direct end-use applications. The inventive polymer is useful in 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 rotational molding processes. Compositions comprising the inventive polymer can also be formed into articles manufactured using conventional polyolefin processing techniques.
    [110] Other applications suitable for the inventive polymer include films and elastic fibers; soft-touch products, such as toothbrush handles and instrument handles; gaskets and profiles; adhesives (including hotmelt adhesives and pressure sensitive adhesives); footwear (including shoe soles and shoe liners); car profiles and interior parts; foam products (both open and closed cells); impact modifiers for other thermoplastic polymers such as high density polyethylene, isotactic polypropylene, or other olefinic polymers; coated cloths; hoses; piping; window strips; helmet coverings; and viscosity index modifiers, also known pour point modifiers, for lubricants.
    [111] Additional treatment of the polymer of this invention can be performed for application in other end uses. For example, dispersions can also be formed (both aqueous
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    23/45 as non-aqueous) using the present polymers, as disclosed in PCT publication No. 2005/021622 (Strandeburg, et al.). The inventive polymer can also be cross-linked by any known means, such as using peroxide, electron beam, silane, azide, or other cross-linking technique. The inventive polymer can also be modified chemically, for example, by grafting (for example, by using maleic anhydride (MAH), silanes, or other grafting agent), halogenation, amination, sulfonation, or other chemical modification.
    Definitions [112] Unless stated to the contrary, implicit in context, or customary in the technique, all parts and percentages are based on weight. For United States patent practice purposes, the contents of any patent, patent application, or publication referred to herein are hereby incorporated by reference in their entirety (or the equivalent US version thereof is also incorporated by reference) especially with respect to the dissemination of synthetic techniques, definitions (to the extent not inconsistent with any definitions provided herein) and general knowledge of the technique.
    [113] In this disclosure, the numerical ranges are approximate and, therefore, may include values outside the range, s target if indicated differently. The numerical ranges include all values of the same, including the lower value and the upper value, in increments of one unit, as long as there is a separation of at least two units between any lower value and any higher value. As an example, if a composition, physical or other property
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    24/45 property, such as, for example, molecular weight, melt index, etc., is from 100 to 1000, it is intended that all individual values, such as 100, 101, 102, etc., and sub-ranges, such as 100 to 144, 155 to 170, 197 to 200, etc., are expressly listed. For ranges containing values less than one (1) or containing fractional numbers greater than one (1) (for example, 1.1, 1.5, etc.), a unit is considered to be 0.0001, 0.001 or 0.1, when appropriate. For ranges containing single-digit numbers less than ten (for example, 1 to 5), a unit is considered to be 0.1. These are just examples of what is specifically intended, and all possible combinations of numerical value between the minimum and the maximum listed value are considered to be expressly stated in this disclosure. Within this disclosure, numerical ranges are provided for, among other things, density, melt index, molecular weight, quantities of reagents and process conditions.
    [114] When used here, the term composition means a combination of two or more materials. With respect to the inventive polymer, a composition is the inventive polymer combined with at least one other material, for example, an additive, filler, another polymer, catalyst, etc.
    [115] When used herein, the terms, polymeric mixture or mixture, mean an intimate physical mixture (that is, without reaction) of two or more polymers. A mixture may or may not be miscible (not separated by phases at the molecular level). A mixture may or may not be separated into phases. A mixture may or may not contain one or more domain configurations, determined by transmission spectroscopy
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    25/45 electronics, light scattering, X-ray scattering, and other methods known in the art. The mixture can be prepared by physically mixing the two or more polymers at the macro level (for example, melted mixed composition or resins) or at the micro level (for example, simultaneous formation within the same reactor).
    [116] The term polymer refers to a compound prepared by polymerizing monomers of either the same or different types. Therefore, the generic term polymer encompasses both the term homopolymer (which refers to polymers prepared from only one type of monomer, with the understanding that traces of impurities can be incorporated into the polymeric structure), and the term interpolymer defined below.
    [117] 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 are polymers prepared from two different monomers), and polymers prepared from more than two different types of monomers.
    [118] The term ethylene-based polymer or ethylene polymer refers to a polymer comprising a majority of ethylene polymerized based on the weight of the polymer, and optionally, may comprise at least one comonomer.
    [119] The term ethylene-based interpolymer or ethylene interpolymer refers to an interpolymer that comprises a majority amount of ethylene polymerized based on the weight of the interpolymer, and comprises at least one comonomer.
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    26/45 [120] The term “reactor zone” refers to a section of a reactor where a polymerization reaction via free radicals occurs by injecting an initiator system, which is capable of decomposing the radicals under conditions within the zone. A reactor zone can be a separate reactor unit or a part of a larger reactor unit. In a tubular continuous flow reactor unit, each zone starts where a new initiator is injected. In an autoclave reactor unit, the zones are formed by a separation device, for example, a baffle, preventing counter-mixing. Each reactor zone has its own starter feed, while feeds of ethylene, comonomer, chain transfer agent and other components can be transferred from a previous reaction zone, and / or freshly injected (mixed or as separate components).
    [121] The term zone reaction product refers to the ethylene-based polymer prepared under high pressure conditions (for example, a reaction pressure greater than 100 MPa) through a polymerization mechanism via free radicals. Due to the transfer of intermolecular hydrogen, dead polymer molecules leaving can be restarted, resulting in the formation of long chain branches (LCB) in the original (linear) polymer main chain. In a reactor zone, new polymeric molecules are initiated, and a portion of the polymeric molecules formed will be grafted into the existing polymeric molecules to form long chain branches. Zone reaction product is defined as the polymer present at the end of the reactor zone.
    [122] The term polymerization conditions refers to the process parameters under which the initiator that enters ba
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    27/45 reactor zone will decompose at least partially into radicals, initiating polymerization. Polymerization conditions include, for example, pressure, temperature, reagent and polymer concentrations, residence time and distribution, which influence the molecular weight distribution and polymer structure. The influence of polymerization conditions on the polymeric product is well described and shown in S. Goto et al., Ref. N ° 1.
    [123] The term “CTA system includes a single CTA or a mixture of CTAs. A CTA system includes a component capable of transferring a hydrogen atom to a growing polymer molecule containing a radical through which the radical is transferred to the CTA molecule, which can then start the departure of a new polymer chain. CTA is also known as telogen or telomer. In a preferred embodiment of the invention, each CTA system comprises a single CTA.
    [124] The term “suction for a hyper-compressor refers to the final compressor before the reactor that conducts one or more feed streams to reactor pressure from a lower pressure. The suction for a hyper-compressor is the input configuration of this compressor.
    [125] The term “hyper-compressor discharge” refers to the output configuration of the hyper-compressor.
    [126] The terms "comprising," including, "having and the like are not intended to exclude the presence of any additional component, step or procedure, whether or not it is specifically disclosed herein. In order to avoid any doubt, all processes claimed here using the term “comprising may include one or more
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    28/45 plus additional steps, pieces of equipment or component parts, and / or materials unless otherwise stated. On the other hand, the term essentially consists of excluding any other component, step or procedure from the scope of any subsequent mention, except those that are not essential to operability. The term consisting of excludes any component, step or procedure not specifically described or listed. The term or, unless otherwise stated, refers to members listed individually as well as in any combination.
    [127] The term containing is not intended to exclude the presence of any additional component, step or procedure, whether or not it is specifically disclosed. In the context of a reaction zone containing a CTA system, the term containing is not intended to exclude the presence of any CTA system not specifically specified.
    Testing methods
    Polymer test methods [128] Density: Samples for density measurement are prepared according to ASTM D1928. The samples are pressed at 190 ° C and 30,000 psi for 3 minutes, and then at 21 ° C and 207 MPa for 1 minute. Measurements are performed up to 1 hour of sample pressing using ASTM D792, Method B.
    [129] Melting index: Melting index, or I 2 , (g / 10 min) is measured according to ASTM D 1238, Condition 190 ° C / 2.16 kg. I 10 is measured according to ASTM D 1238, Condition 190 ° C / 10 kg, on a plate with an assembled tension cylinder, and a traction cylinder controlled by a stepper motor. The plastomer produces a row of molten polymer that is guided around the
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    29/45 tensioner cylinder on the scale plate and even on another pulley before being wound on the traction cylinder. The traction cylinder speed is precisely controlled by computer. The melt elasticity is determined as the force on the tensioning cylinder at a specified stretch ratio (drag speed / die exit speed). The technology is applicable to thermoplastic and / or thermoset plastics.
    [130] Melt elasticity: The melt elasticity is measured using a DMELT system. The DMELT system comprises a commercial plastomer, a digital scale incorporating a heavy sample of use. The samples are prepared for density measurement according to ASTM D 1928. The samples are pressed at 190 ° C and 30,000 psi for 3 minutes, and then at 21 ° C and 207 MPa for 1 minute. Measurements are performed up to 1 hour of sample pressing using ASTM D792, Method B.
    [131] For the measurement of melt elasticity, a row of melted standard plastomer polymer (MP600 Extrusion Plastomer (Melt Indexer) System Installation & Operation Manual (# 020011560), Tinius Olsen, 1065 Easton Road, Horsham, PA 19044 is extruded -8009; Ref. No. 13.6) drum at a constant temperature (190 ° C) through a standard MFR matrix of ASTM D1238 (hole height (8,000 ± 0, 025 mm) and diameter (2.0955 ± 0.005 mm)) using a heavy piston. The extrudate is pulled through a series of free spinning cylinders on a cylinder driven by a stepper motor (Stepper Motor and Controller Operating Manual, Oriental Motor USA Corporation, 2570 W 237 th Street, Torrance, Ca 90505; Ref. N ° 13.7 ) that increases throughout a speed range during the analysis. Registers to
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    30/45 strength of the polymer row pulled on a tensioning cylinder mounted on the scale platform (Excellence Plus XP Precision Balance Operating Instructions, Mettler Toledo, 1900 Polaris Parkway, Columbus, Ohio 43240; Ref. No. 13.8) by the integrated control computer. From a linear regression of the acquired force data, the final informed value is determined based on a constant speed ratio (33.2) or deformation (Ln [speed ratio] = 3.5) of the row speed of polymer against matrix outlet speed. The analysis results are reported in cN (centiNewton).
    [132] Triple detector gel permeation chromatography (TDGPC): 3Det-GPC analysis at high temperature is performed on an Alliance GPCV2000 instrument (Waters Corp.) set at 145 ° C. The flow rate for the GPC is 1 mL / min. The injection volume is 218.5 pL. The column set consists of four Mixed-A columns (20 gm particles; 7.5 x 300 mm; Polymer Laboratories Ltd).
    [133] Detection is achieved using a Polymer Char IR4 detector, equipped with a CH sensor; a Wyatt Technology Dawn DSP MALS detector (Wyatt Technology Corp., Santa Barbara, CA, USA), equipped with a 30 mW argon ion laser operating at λ = 488 nm; and a Waters three capillary viscosity detector. The MALS detector is calibrated by measuring the spreading intensity of the TCB solvent. The normalization of photodiodes is done by injecting SEM 1483, a high density polyethylene with a weight average molecular weight (Mw) of 32,100 and polydispersion of 1.11. An increment of specific refractive index (dn / dc) of -0.104 mL / mg is used for polyethylene in TCB.
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    31/45 [134] Conventional GPC calibration is done with 20 narrow PS standards (Polymer Laboratories Ltd.) with molecular weights in the range of 580-7,500,000 g / mol. The maximum molecular weights of polystyrene standard are converted to molecular weights of polyethylene using the equation M polyethylene A x (M polystyrene) where A ~ 0.39, and B = 1. The value of A is determined using HDPE Dow 53494 -38-4, a linear polyethylene homopolymer with 115,000 g / mol Mw. The HDPE reference material is also used to calibrate the IR detector and viscometer admitting 100% mass recovery and an intrinsic viscosity of 1,873 dL / g.
    [135] 1,2,4-trichlorobenzene grade “Baker analyzed distillate (JT Baker, Deventer, Netherlands) containing 200 ppm 2,6-ditherciobutyl-4-methyl phenol (Merck, Hohenbrunn, Germany) is used as the solvent for sample preparation, as well as for the 3Det-GPC experiments. HDPE SRM 1483 is obtained from U.S. National Institute of Standards and Technology (Gaithersburg, MD, USA).
    [136] Solutions are prepared in LDPE dissolving at samples in mild agitation per three 160 hours ° C. Dissolve up OS standards in same conditions by 30 minutes. The sample concentration To the experiments in 3Det-GPC is 1.5 mg / mL and the concentrations polystyrene
    0.2 mg / ml.
    [137] A MALS detector measures the scattered signal of polymers or particles in a sample at different scattering angles θ. The basic light scattering equation (by M. Andersson, B. Wittgren, K. G. Wahlund, Anal. Chem. 75, 4279 (2003)) can be written as:
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    32/45
    16π 2 I 2. 2 (θΊ
    3λ 2 M UJ (2) where Rq is the Rayleigh excess ratio, K is an optical constant, which among other things depends on the specific increment of the refractive index (dn / dc), c is the solute concentration, M is the molecular weight, R g is the radius of rotation, and λ is the wavelength of the incident light. The calculation of the molecular weight and the radius of rotation of the light scattering data requires extrapolation to zero angle (see also PJ Wyatt, Anal. Chim. Acta 272, 1 (1993)). This is done by assembling a 1/2 (K w / Ro) graph as a function of sen 2 (0/2) called a 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. Zimm and Berry methods are used for all data. The second virial coefficient is admitted to be negligible. The intrinsic viscosity numbers of both concentration and viscosity detector signals are calculated considering the ratio of the specific viscosity and the concentration in each elution slice.
    [138] ASTRA 4.72 software (Wyatt technology Corp.) is used to collect the signals from the IR detector, viscometer, and the MALS detector. Data processing is performed with EXCEL macros from Microsoft home.
    [139] The calculated molecular weight and molecular weight distribution (M w / M n ) are obtained using a light scattering constant derived from one or more of the mentioned polyethylene standards and a concentration coefficient of
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    33/45 index of refraction, dn / dc, of 0.104. Generally, the mass detector response and the light scattering constant should be determined from a linear pattern with a molecular weight in excess of 50,000 Daltons. Viscometer calibration can be performed using the methods described by the manufacturer or, alternatively, using the published values of appropriate linear standards such as those of Standard Reference Materials (SRM) 1475a, 1482a, 1483, or 1484a. It is assumed that the chromatographic concentrations are low enough to eliminate the treatment of effects of the 2nd viral coefficient (effects of concentration on the molecular weight).
    Film test conditions [140] Light diffusion: Samples measured for light diffusion (fogging) are tested and prepared according to ASTM D 1003. The films are prepared as described in the experimental section below.
    [141] Brightness at 45 ° and 60 °: Brightness at 45 ° and 60 ° is measured by ASTM D-2457. The films are prepared as described in the experimental section below.
    Experimental
    Calculations for Z1, Z2 and Zi:
    [142] The “molar concentration of a CTA j reactor in a reaction zone i ([CTA] ji) is defined as the“ total molar quantity of that CTA recently injected in reactor zones 1 ai divided by the “molar quantity total ethylene recently injected in reactor zones 1 to i. This reaction is sampled below in Equation A.
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    34/45 i
    lL n CTAJ k [CTA] j = ----- k = 1 (Equation A) [143] In Equation A, j> 1, n CTA < j is the amount of moles of the j-th CTA recently injected into i -th reactor zone en et h is the quantity of moles of ethylene recently injected in the i-th reactor zone.
    [144] the activity of a CTA (system) in a reactor zone i is defined as the sum of the molar concentration of reactor zone of each CTA in the reactor zone multiplied by its chain transfer activity constant (Cs). The chain transfer activity constant (Cs) is the ratio of reaction rates Ks / Kp, at a reference pressure (1360 atm) and at a reference temperature (130 ° C). This relationship is shown below in Equation B, where n compi is the total number of CTAs in the reactor zone i.
    n co mp .i / pi n, -C, j
    · '(Equation B) [145] Consequently, the Zl / Zi ratio in Equation C is shown below.
    ftçompj (Equation C) [146] Table A shows the values of the constant of
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    35/45 chain transfer (Cs) for some chain transfer agents exhibiting Mortimer-derived chain transfer constants (Cs) at 130 ° C and 1360 atm for examples of chain transfer agents.
    Table A - Cs values measured by Mortimer at 130 ° C and 1360 atm in References 3 and 4
    CTA Cs at 130 ° C and 1360 atm Propane 0.0030 Isobutane 0.0072 Propylene 0.0122 Isopropanol 0.0144 Acetone 0.0168 1-Butene 0.047 Methyl ethyl ketone 0.060 Propanal (propionic aldehyde) 0.33 Terciobutanothiol 15
    [147] Ref. No. 2: G. Mortimer; Journal of Polymer Science: Part A-1; Chain transfer in ethylene polymerization; vol. 4, p 881-900 (1966).
    [148] Ref. No. 3: G. Mortimer; Journal of Polymer Science: Part A-1; Chain transfer in ethylene polymerization. Part IV. Additional study at 1360 atm and 130 ° C; vol. 8, p 15131523 (1970).
    [149] Ref. No. 4: G. Mortimer; Journal of Polymer Science: Part A-1; Chain transfer in ethylene polymerization. Part VII. Very reactive and depletable transfer agents; vol. 10, p
    163-168 (1972). [150] When only one CTA is used in the reactor system total, Equations B and C are simplified, respectively, to the Equations D and E.Z ^ CTA ^ C,
    (Equation D)
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    Z x _ [CTA] X C S _ [CTA} X z t [CTA i -C s CTA} t (Equation E) [151] Four reactor zones configured as A are used
    AT T. Reactor zone 1 is A, reactor zone 2 is A, reactor zone 3 is Τ Λ reactor zone 4 is T. CTA is injected into zones 1 and 2; only initiator is injected in zones 3 and 4, however, typically some CTA is extended in zones 3 and 4 of zones 1 and 2. No CTA is added in reactor zones 3 and 4.
    [152] Only one CTA implies that Cs falls outside the equations, and therefore Equation E is used for most examples, as shown below.
    [CTAy · C s _ [CL4] 1 _ z 2 [CTA} 2 C s [CTA} 2
    Eth n eth k k = -
    Eth n eth k k = _____ lL n CTA k k =
    Σ ^ Μ ZCT4 £ = 1 _____ £ = 1 ______
    1 '2 £ = 1k = * ^ eth ^ ^ etl ^
    Weth n CTA, n CTA, + [153] In addition, the tubular part of the AC / tube reactor system (which is the system used to generate all the examples) can be considered as reactor zones 3 and 4, where both the zones do not receive any CTA or ethylene injected recently. This means that Equation E becomes as shown below. Thus, Zl / Z4 = Zl / Z3 = Z1 / Z2.
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    Z 1 = [CTA] V C S [CTA ^
    Zi [CT / íh-C, [CTAl = a ± i _____
    Σ ”* ϊ * = 1 /
    * = 1 i
    Σ η ΟΓΑ>
    * = 1 i
    Σ η * κ Σ n CTA t k = l * = 1 i 1 2
    Σ n 'LHT CTAk Σ n Σ n ELH "_ 1 = A * = _ * 1 = 1
    Σ ^.
    * = 1
    Σ ^ τα, * = 1 _ Z 1
    V Z2 Λ n CTA t * = 1 [154] Furthermore, for all examples n and thi = n and th2f and r therefore, the relationship is still simplified as shown below.
    Z 1 _ n eth, + n CTA, _ ^ 2 n et n CTA, + n CTA 1 n elh, + n eth, n CTA, _ ncTA >
    n eth, n CTA, + n CTA 2 n CTA, + CT / Ç
    Polymerization and polymers [155] Comparative Example 1: Formation MEK (CTA) is equally divided by both autoclave reaction zones (1 and 2).
    [156] Reactor pressure: 2450 bar [157] Autoclave dwell time (AC); 55 seconds [158] Dwell time in tubular: 80 seconds [159] Terciobutyl peroxy perpoxate (TBPV) is injected as an initiator via free radicals into each autoclave reactor zone. At the beginning of the two reactor zones of the tubular reactor, a mixture of terciobutyl peroxy-2-ethyl hexanoate (TBPO) and ditherciobutyl peroxide (DTBP) is injected as an additional free radical initiator.
    Temperature conditions:
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    [160] Upper zone in autoclave (50% in ethylene): Input: 37 ° C; control 185 ° C [161] Lower zone in autoclave (50% in ethylene): Input: 35 ° C; control 185 ° C . [162] Control from 1 to zone tube length: 274 ° C [163] 2nd Control zone tube length: 274 ° C [164] Methyl is used ethyl ketone (MEK) how O agent of
    chain transfer. The recycled MEK (after partial conversion in the reactor, partial condensation in the low pressure recycling section and / or partial purge) is divided equally by both reactor ethylene feed streams and both AC reaction zones. The new training MEK (to maintain MEK concentration in order to control / vary MI) is equally divided by both AC reaction zones. Product sampling [165] Samples are taken to measure polymer rheology results, and a sample (1b) is collected for evaluation of expanded film and extrusion coating. The results are reported in Table 1.
    Table 1. Results of rheology of Comparative Examples 1a1b and MEK concentrations.
    Sample Fusion index Cast elasticity Zone 1 MEK (AC) power Zone 2 MEK (AC) power Z1 / Z2 Z1 / Zndg / min cN molar ppm molar ppm 1a 5, 09 1.65 4610 4610 1.00 1.00 1b 4.94 1.67 4852 4852 1.00 1.00
    [166] Inventive example 2: forming MEK is sent to the upper autoclave reaction zone.
    [167] Reactor pressure: 2450 bar [168] Autoclave time: 55 seconds
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    39/45 [169] Dwell time in tubular: 80 seconds [170] Inject tert-butyl peroxy perpivalate (TBPV) as an initiator via free radicals into each autoclave reactor zone. At the beginning of the two reactor zones of the tubular reactor, a mixture of terciobutyl peroxy-2-ethyl hexanoate (TBPO) and ditherciobutyl peroxide (DTBP) is injected as an additional free radical initiator.
    Temperature conditions:
    [171] Upper zone autoclave (50% of ethylene new): Input: 37 ° C; control 185 ° C [172] Lower zone autoclave (50% of ethylene new): Input: 35 ° C; control 185 ° C. [173] Control from 1 to tube zone : 274 ° C [174] 2nd Control tube zone : 274 ° C [175] Methyl is used ethyl ketone (MEK) as the agent of
    chain transfer. The recycled MEK (after partial conversion in the reactor, partial condensation in the low pressure recycling section and / or partial purge) is divided equally by both reactor ethylene feed streams and both AC reaction zones. The new forming MEK (to maintain MEK concentration in order to control / vary MI) is fed into the ethylene feed stream sent to the upper autoclave zone.
    Product sampling [176] Samples are taken to measure the polymer rheology response, and a sample (2c) is collected for evaluation of expanded film and extrusion coating. The results are reported in Table 2.
    Table 2. Results of Example 2 rheology and MEK concentrations.
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    Sample Fusion index Cast elasticity Zone 1 MEK (AC) power MEK (AC) powerZone 2 Z1 / Z2 Z1 / Zndg / min cN molar ppm molar ppm 2a 3.28 2.89 3919 5783 0.81 0.81 2b 4.32 2.26 4124 6116 0.81 0.81 2c 4.60 2.05 4122 6082 0.81 0.81
    [177] Comparative example 3: Formation propylene (CTA) is equally divided by both reaction zones of
    autoclave (1 and 2). [178] Ballast pressure: 2000 Pub [179] Lenght of stay in autoclave (AC) : 55 seconds. [180] Length of stay in tubular: 80 seconds.[181] Peroxy perpivalate is injected from terciobutila (TBPV)
    as an initiator via free radicals in each autoclave reactor zone. At the beginning of the two reactor zones of the tubular reactor, a mixture of terciobutyl peroxy-2-ethyl hexanoate (TBPO) and ditherciobutyl peroxide (DTBP) is injected as an additional free radical initiator.
    Temperature conditions:
    [182] Upper autoclave zone (50% new ethylene):
    Inlet: 40 ° C; 202 ° C control [183] Lower autoclave zone (50% new ethylene):
    Inlet: 36 ° C; control 236 ° C.
    [184] Control tube 1 zone: 275 ° C [185] Control tube second zone: 275 ° C [186] Use is propylene as chain transfer agent. The recycled propylene (after partial conversion in the reactor, partial condensation in the low pressure recycling section and / or partial purge) is divided equally by both
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    41/45 reactor ethylene feed streams and both AC reaction zones. The new forming propylene (to maintain propylene concentration in order to control / vary MI) is divided equally by both AC reaction zones. Product sampling [187] Samples are taken to measure the polymer rheology response, and expanded film evaluation. The results are reported in Table 3.
    Table 3. Results of comparative Example 3 rheology and propylene concentrations.
    Sample Fusion index Cast elasticity MEK (AC) powerZone 1 MEK (AC) powerZone 2 Z1 / Z2 Z1 / Zndg / min cN molar ppm molar ppm 3 1, 07 13, 10 16120 16120 1.00 1.00
    [188] Inventive example 2: Formation propylene is sent to the lower autoclave reaction zone.
    [189] Reactor pressure: 2000 bar [190] Autoclaving time: 55 seconds [191] Tubing time: 80 seconds [192] Tertiarybutyl perpivalate peroxy (TBPV) is injected as a free radical initiator in each autoclave reactor zone. At the beginning of the two reactor zones of the tubular reactor, a mixture of terciobutyl peroxy-2-ethyl hexanoate (TBPO) and ditherciobutyl peroxide (DTBP) is injected as an additional free radical initiator.
    Temperature conditions:
    [193] Zone higher in autoclave (50% in ethylene new): Input: 40 ° C; control 204 ° C [194] Zone bottom in autoclave (50% in ethylene new): Input: 36 ° C; control 237 ° C.
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    42/45 [195] Control tube 1 zone: 276 ° C [196] Control tube second zone: 275 ° C [197] Use is propylene as chain transfer agent. The recycled propylene (after partial conversion in the reactor, partial condensation in the low pressure recycling section and / or partial purge) is divided equally by both reactor ethylene feed streams and both AC reaction zones. The new forming propylene (to maintain propylene concentration in order to control MI) is fed into the ethylene feed stream sent to the lower autoclave zone.
    Product sampling [198] Samples are taken to measure the rheology response and expanded film evaluation. The results are reported in Table 4.
    Table 4. Results of Example 4 rheology and propylene concentrations.
    Sample Fusion index Elasticity and cast Propylene (AC) supply Zone 1 Propylene (AC) supply Zone 2 Z1 / Z2 Z1 / Zndg / min cN molar ppm molar ppm 4 0.97 13, 65 12350 16370 0.86 0.86
    Table 5. Example polymers properties
    Example No. Z1 / Z2 Density (kg / m 3 ) M w / Mn MI (dg / min) ME(cN) Ex. Comp. 1b 1.00 929 5, 15 4.94 1.67 Example 2c 0.81 929 5.99 4.60 2.05 Ex. Comp. 3 1.00 919 9, 62 1, 07 13, 10 Example 4 0.86 920 10, 30 0.97 13, 65
    Polymers and films [199] Each of the films was formed using the process parameters shown in Table 6. The inventive film 1 was prepared from the polymer of Example 2c.
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    The inventive film 2 was prepared from the polymer of Example 4.
    [200] Comparative film 1 was prepared from a sample of Comparative Example 1.
    [201] Comparative film 2 was prepared from a sample of Comparative Example 3.
    [202] All films are prepared with a “25/1 chromium-spindle (3/1 compression ratio; 10D feed zone; 3D transition zone; 12D measurement zone) connecting to a 25 mm matrix in diameter. No internal bubble cooling was used. Table 8 shows the general expanded film parameters used to produce the film. The same conditions were used for all examples and comparative examples. Drum 1 of the temperature profile is the closest to the pellet feeding funnel followed by Drum 2, which is followed by Drum 3, which is followed by Drum 4. The thickness of the films was measured with a micrometer.
    Table 6. Manufacturing conditions for expanded films.
    ParameterExplosion ratio (BUR) 2.75 Output (production) (kg / h) 1, 8 Film thickness (pm) 50 ± 1.0 Matrix slit (mm) 0, 8 Air temperature (° C) 23 Temperature profile (° C)Drum 1 150 Drum 2 165 Drum 3 175 Drum 4 175 Matrix 175
    [203] Tables 7 and 8 below and Figures 2-3 show, respectively, the films and their optical properties. All means and standard deviations are based on 10 measurements per
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    44/45 sample.
    Table 7. Optical properties of expanded film samples from Comparative Example 1d and Example 2e.
    Example No. Light diffusion (%) 45 ° brightness (%) Comparative Example1b 9.9 ± 0.4 54.7 ± 1.8 Example 2c 11.6 ± 0.4 49, 3 ± 2.4
    Table 8. Optical properties of expanded film samples from Comparative Example 3 and Example 4.
    Example No. Light diffusion (%) 45 ° brightness (%) Comparative Example3 28, 1 ± 0.7 15, 1 ± 1.9 Example 4 35, 9 ± 0.7 13.8 ± 1.8
    Polymers and extrusion coating [204] Extrusion coating was performed in Comparative Example 1b and Example 2c. The melt index of Comparative Example 3 and Example 4 is too low for a good coating operation. Each of the coatings was formed according to the following conditions. The resins were extruded at an adjusted extruder temperature of 320 ° C from a hanger-type extrusion die with a nominal 0.7 mm die slit, on 70 g / m 2 Kraft paper in an amount of 25 g / m 2 in parts with in-process addition of aluminum foils of 40 pm, using a 250 mm air gap and variable line speeds in meters per minute, and at a line speed of 100 m / min, but with variable air slits, using a finished chilled lamination cylinder maintained at a temperature of 15 to 20 ° C.
    [205] Inventive coating 1 was prepared from a sample of the polymer of Comparative Example 1b. Table 9 below shows the results of coatings. Stretch is the maximum line speed attainable during stable coating. Narrowing is the contraction in the width of the web in
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    45/45 compared to the matrix width at fixed line speed (100 m / min). Smaller narrowing and longer stretching are both very desirable. Smaller narrowing means better dimensional stability of the web, which, in turn, provides better control of the coating on the substrate. Greater stretch means greater line speed, which in turn means better productivity.
    Table 9. Extrusion coating properties of
    Comparative Example 1b and Example 2c.
    Example No. Stretch (m / min) Narrowing (mm) Comparative Example 1b 100 251 Example 2c 680 207
    [206] Although the invention has been described in certain details through the previous description of the preferred embodiments, these details are for the primary purpose of illustration. Many variations and modifications can be made by a person skilled in the art without departing from the spirit and scope of the invention described in the following claims.
    权利要求:
    Claims (14)
    [1]
    1. High pressure polymerization process to form an ethylene-based polymer, characterized by the fact that it comprises the steps of:
    (A) Inject a first feed comprising ethylene and, optionally, a chain transfer agent system (CTA system) in a first autoclave reactor zone operating under polymerization conditions to produce a first zone reaction product, the CTA of the first reactor zone having a transfer activity Z1; and (B) (1) Transfer at least part of the reaction product from the first zone to a second reactor zone selected from a second autoclave reactor zone or a tubular reactor zone and operating under polymerization conditions, and (2) inject recently a second feed in the second reactor zone to produce a second zone reaction product,
    - with the proviso that the second reactor zone contains a CTA system having a transfer activity Z2; and
    - with the proviso that the Z1 / Z2 ratio is less than 1.
    [2]
    2. Process, according to claim 1, characterized by the fact that it also comprises one or more steps of transferring a zone reaction product produced in a (i - th - 1) reaction zone to an i-th reaction zone, where 3 <i <n, en> 3, each zone operating under polymerization conditions, and optionally adding an i-th feed comprising a CTA system in the i-th reaction zone, the CTA system of the i-th reaction zone having a transfer activity of Zi with the proviso that the ratio of Z1 / Zi <1 to all i <ne Z1 <Zn.
    Petition 870190057554, of 6/21/2019, p. 50/55
    2/3
    [3]
    Process according to either of claims 1 or 2, characterized in that the second or i-th feed comprises at least one comonomer selected from the group consisting of acrylate, silane, vinyl ester, unsaturated carboxylic acid and monoxide of carbon.
    [4]
    4. Process according to any of the claims of
    1 to 3, characterized by the fact that at least one of the feeds for at least one of the reactor zones contains a CTA that is different from at least one of the CTAs of the other reactor zones.
    [5]
    5. Process according to claim 4, characterized in that each CTA is, independently, one of an olefin, an aldehyde, a ketone, an alcohol, a saturated hydrocarbon, an ether, a thiol, a phosphine, an amino , an amine, an amide, an ester, and an isocyanate.
    [6]
    6. Process according to any of the claims of
    1 to 5, characterized by the fact that at least one CTA has a Cs chain transfer constant greater than 0.001.
    [7]
    7. Process according to any of the claims of
    1 to 6, characterized by the fact that each of the polymerization conditions in the reactor zones comprises, independently, a temperature greater than or equal to 100 ° C less than 400 ° C, and a pressure greater than or equal to 100 MPa less than 500 MPa.
    [8]
    8. Process according to any of the claims of
    1 to 7, characterized by the fact that the ratio of Z1 / Zi <1 for all i <n and Z1 / Zn <0.95.
    [9]
    9. Process according to any of the claims of
    1 to 8, characterized by the fact that the ratio of Z1 / Zi <1 for all i <n and Z1 / Zn <0.90.
    Petition 870190057554, of 6/21/2019, p. 51/55
    3/3
    [10]
    10. Ethylene-based polymer, characterized by the fact that it is prepared by the process as defined by any one of claims 1 to 9.
    [11]
    11. Ethylene-based polymer, characterized by the fact that it comprises the following properties: (1) a melt elasticity, in centiNewton (cN) less than or equal to (8.1 x (melt index) -0.98 ), a melt index greater than 3 g / 10 min, and a density of 0.926 to 0.935 g / cm 3 .
    [12]
    12. Ethylene-based polymer according to claim
    11, characterized fur fact of the elasticity in fused, in centiNewton (cN), to be less than or equal to (9, 3 x (index in -0.98 ). 13. Composition, characterized by the fact in understand O
    ethylene-based polymer as defined by claims 10 to 12.
    [13]
    14. Article, characterized by the fact that it comprises at least one component formed with the composition as defined by claim 13.
    [14]
    15. Film, characterized by the fact that it comprises at least one component formed with the composition as defined by claim 13.
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    同族专利:
    公开号 | 公开日
    KR20120115323A|2012-10-17|
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    CN102762609A|2012-10-31|
    BR112012015026A2|2017-07-04|
    ES2555498T3|2016-01-04|
    CA2784272A1|2011-06-23|
    JP2013514440A|2013-04-25|
    EP2513162B1|2015-11-04|
    WO2011075465A1|2011-06-23|
    EP2513162A1|2012-10-24|
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    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-04-24| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2019-09-03| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2019-11-05| 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 14/12/2010, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
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    US64198509A| true| 2009-12-18|2009-12-18|
    PCT/US2010/060244|WO2011075465A1|2009-12-18|2010-12-14|Polymerization process to make low density polyethylene|
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