• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    HIGH PRESSURE POLYMERIZATION PROCESS TO FORM A POLYMER BASED ON ETHYLENE, POLYMER BASED ON ETHYLENE, COMPOSITION AND ARTICLE. A high pressure polymerization process to form an ethylene-based polymer comprises the steps of: (A) Injecting a first feed comprising a chain transfer agent system (CTA system) and ethylene 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 Zl 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 from a tubular reactor zone and operating under polymerization conditions, and optionally ( 2) Inject a second new feed into the second reactor zone to produce a second zone reaction product, with the proviso that at least one of the first reactor zone product and the newly injected feed comprises a CTA system with an activity of transfer Z2; and with the proviso that the ratio of Z1: Z2 is greater than (...).
    公开号:BR112013007510B1
    申请号:R112013007510-4
    申请日:2011-09-21
    公开日:2020-10-20
    发明作者:Otto J. Berbee；Cornelis F. J. Den Doelder；Cornelis J. Hosman
    申请人:Dow Global Technologies Llc；
    IPC主号:
    专利说明:

    Field of invention
    [001] This invention relates to low density polyethylene (LDPE) and polymerization improvements to prepare LDPE. Notably, the polymerization process involves autoclaves reactors, preferably operating sequentially with tubular reactors. History of the invention
    [002] There are many types of polyethylene produced and sold today. In particular, a type is prepared by several suppliers and sold in large quantities. This polyethylene is called polyethylene via high pressure free radicals (usually called LDPE), and is usually prepared using a tubular reactor, or an autoclave reactor, or sometimes a combination. Sometimes polymer users mix LDPE with other polymers, such as linear low density polyethylene (LLDPE), to try to modify properties, such as fluidity, processability or density. However, there is a need for new LDPE polymers, which can have improved optical properties of films, while maintaining other performance attributes.
    [003] Low density polyethylene resins with higher densities (greater than or equal to (>) 926 kg / m3) are produced at reduced polymerization temperature and high pressure, in order to reduce the frequency of short chain branching, and consequently increase the density of the product. Table A shows the kinetic data in the reaction steps involved, derived from S. Goto et al .: Journal of Applied Polymer Science: Applied Polymer Symposium, 36, 21- 40, 1981 (Title: Computer model for commercial high pressure polyethylene reactor base on elementary reaction rates obtained experimentally) (Title: Computational model for commercial high pressure polyethylene reactor based on elementary reaction rates obtained experimentally) (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. For polymer properties the ratio between the rate of a given reaction step and the rate of propagation is of importance. Table A. Rate constants of elementary reaction rates determined by Goto et al. (Reference N ° 1)

    [004] The characteristic temperature dependence is expressed by Δ Activation energy, thus for SBC frequency in product: Δ Activation energy = 13.03 - 10.52 = 2.51 kcal / mol.
    [005] In the production of medium density high pressure resins, low temperature conditions must be applied in order to reduce short chain branching. With the kinetic data of Goto et al., It was discovered that a "density of 930 kg / m3" can be produced keeping the average polymerization temperature at 205 ° C, for a reactor system operating at 2400 bar. This low average temperature can be achieved by lowering the control temperature in each zone of an autoclave process, and lowering the maximum control temperatures in a tubular reactor. The low control / maximum temperatures required to produce medium resins in a tubular reactor result in significantly reduced heat transfer capacity, and consequently, significantly reduced conversion. For example, an average polymerization temperature of 175 ° C for the first polymeric fraction of a tubular reactor, where polymerization starts at 150 ° C, leads to a sensitive heat content of 50 ° C, necessary to dissipate the polymerization heat , which in turn is equivalent to a conversion of just 4%.
    [006] The conversion of a tubular / autoclave reactor can be maintained at a much higher level, since this system depends on a greater extension in the sensitive heat content, which allows to prepare a large part of the polymer in very low temperature conditions . However, an average polymerization temperature of 175 ° C for the first polymeric fraction of an autoclave reactor leads to a sensitive heat content of 135 ° C, which is equivalent in adiabatic conditions to a conversion of only 10%.
    [007] Despite the significantly lower conversion level, medium density tubular reactor products are still preferred in many expanded film applications to obtain better optical film properties due to a narrower molecular weight distribution. The molecular weight distribution of autoclave and autoclave / tube products is increased by increasing the frequency of long chain branching (LCB) (due to the higher conversion and level of polymer concentration) and the long residence time in the reactor system global. In an autoclave system, some polymeric molecules will remain, and will continue to grow very long through the long chain branching mechanism, while other polymeric molecules will remain and grow very short. The global impact of the wide distribution of extended residence time of the molecular weight distribution.
    [008] As discussed above, there is a need for narrow MWD polyethylene products, with improved optical properties, which can be prepared at high levels of conversion in autoclave or autoclave / tube reactor systems. These and other needs were met by the following invention. Summary of the invention
    [009] The invention provides a high pressure polymerization process to form an ethylene-based polymer, the process comprising the steps of: (A) Injecting a first feed comprising a chain transfer agent system (CTA system) and ethylene 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 Zl 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 from a tubular reactor zone and operating under polymerization conditions, and optionally ( 2) Inject a second new feed into the second reactor zone to produce a second zone reaction product, with the proviso that at least one of the first reactor zone product and the newly injected feed comprises a CTA system with an activity of transfer Z2; and with the proviso that the ratio of Z1: Z2 is greater than 1.
    [0010] The invention also provides an ethylene-based polymer prepared comprising the following properties: (1) a melt elasticity, in centiNewton, less than or equal to (7.0 x (melt index) -0'55) and greater than or equal to (6.0 x (melt index) -0'55) for a polymer with a melt index greater than 0.45 and less than 0.70; or (2) a melt elasticity, in centiNewton, less than or equal to (5.5 x (melting index) -0'83) and greater than or equal to (4.0 x (melting index) ') for a fusion index greater than 2.5 and less than 4.0. In an embodiment, the inventive ethylene-based polymer is prepared by the inventive process. Brief description of the drawings
    [0011] Figure 1 is a graph of melt elasticity (ME) as a function of the melt index (MI) for the samples of Comparative Example 1 and Example 2;
    [0012] Figure 2 is a graph of melt elasticity (ME) as a function of the melt index (MI) for the samples of Comparative Example 3 and Example 4;
    [0013] Figure 3 is a bar graph of optical properties of an expanded film made with the polymer of Comparative Example 1 and an expanded film made with the polymer of Example 2;
    [0014] Figure 4 is a bar graph of optical properties of an expanded film made with the polymer of Comparative Example 3 and an expanded film made with the polymer of Example 4;
    [0015] Figure 5 is a bar graph of optical properties of an expanded film made with the polymer of Comparative Example 5 and an expanded film made with the polymer of Example 6; and
    [0016] Figure 6 is a graph of improved pseudoplasticity index (ESTI) as a function of fusion index (MI) for Comparative Examples 1 and 3 (mean values) and 5, and for Examples 2 and 4 (mean values) and 6. Description of embodiments of the invention Overview
    [0017] As discussed above, the invention provides a high pressure polymerization process to form an ethylene-based polymer, the process comprising the steps of: (A) Injecting a first feed comprising a chain transfer agent system (CTA system) and ethylene 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 Zl 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 from a tubular reactor zone and operating under polymerization conditions, and optionally ( 2) Inject a second new feed into the second reactor zone to produce a second zone reaction product, with the proviso that at least one of the first reactor zone product and the newly injected feed comprises a CTA system with an activity of transfer Z2; and with the proviso that the ratio of Z1: Z2 is greater than 1.
    [0018] In an incorporation, the process further comprises one or more steps of transferring a zone reaction product produced in an (i-th - 1) reaction zone to an i-th zone, where 3 in, and> 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 Zi transfer activity; and with the proviso that the Zl / Zi ratio is greater than 1.
    [0019] In an embodiment, a second feed is injected into the second reactor zone, and the second feed comprises a CTA system.
    [0020] In an incorporation, food in the second food zone does not include an SD
    [0021] In an embodiment, feeding in the second feeding zone comprises ethylene.
    [0022] In an embodiment, feeding in the second feeding zone comprises ethylene <
    [0023] In an incorporation, food in the second food area comprises ethylene, from CTA.
    [0024] In an incorporation, a second reactor is injected, and the second CTA tank. a second reactor is injected, and the second is injected a second reactor, and the second: a CTA system. a second reactor is injected, and the second but does not comprise a second feed system according to any of the previous embodiments comprises at least one comonomer.
    [0025] In an incorporation, the i-th feeding according to any of the previous incorporations also comprises ethylene.
    [0026] In an incorporation, the i-th feeding according to any of the previous incorporations also comprises at least one comonomer.
    [0027] In an embodiment, at least one comonomer according to 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 and autoclave.
    [0028] In an incorporation, the at least one comonomer according to any of the previous incorporations is one among acrylate, silane, vinyl acetate and carbon monoxide.
    [0029] In an incorporation of the process according to any of the previous incorporations, steps (B) (1) and (B) (2) are carried out simultaneously.
    [0030] In an incorporation of the process according to any of the previous incorporations, steps (B) (1) and (B) (2) are carried out at different times.
    [0031] In a process incorporation according to any of the previous incorporations, at least part of the first zone reaction product is transferred to a second autoclave reactor zone.
    [0032] In a process incorporation according to any of the previous incorporations, the second autoclave reactor zone is adjacent to the first autoclave reactor zone.
    [0033] In a process incorporation according to any of the previous incorporations, the second autoclave reactor zone is separated from the first autoclave reactor zone by one or more reactor zones.
    [0034] In a process incorporation according to any of the previous incorporations, at least part of the reaction product from the first zone is transferred to a tubular reactor zone.
    [0035] In a process incorporation according to any of the previous incorporations, the tubular reactor zone is adjacent to the first autoclave reactor zone.
    [0036] In a process incorporation according to any of the previous incorporations, the tubular reactor zone is separated from the first autoclave reactor zone by one or more reactor zones.
    [0037] In a process incorporation according to any of the previous incorporations, each feed for each reactor zone contains the same CTA system. In an additional incorporation, the CTA system for each feed contains a single CTA.
    [0038] In a process incorporation according to 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.
    [0039] In a process incorporation according to 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 ester, and an isocyanate.
    [0040] In a process incorporation according to any of the previous incorporations, each CTA is independently methyl ethyl ketone (MEK), propanoic aldehyde (propanal), butene-1, acetone, isopropanol or propylene.
    [0041] In a process incorporation according to any of the previous incorporations, at least one CTA has a Cs chain transfer constant greater than 0.003.
    [0042] In an incorporation of the process according to any of the previous incorporations, all autoclave zones are located in the same autoclave reactor.
    [0043] In an incorporation of the process according to any of the previous incorporations, the autoclave zones are located in two or more different autoclaves reactors.
    [0044] In an incorporation of the process according to any of the previous incorporations, the autoclave zones are approximately the same size.
    [0045] In an incorporation of the process according to any of the previous incorporations, two or more of the autoclave zones are of different sizes.
    [0046] In a process incorporation according to any of the previous incorporations, the polymerization conditions in each reactor zone are operated at the same temperature and pressure.
    [0047] In a process incorporation according to any of the previous incorporations, at least one polymerization condition in at least one reactor zone is different from the other polymerization conditions.
    [0048] In a process incorporation according to any of the previous incorporations, each of the polymerization conditions in the reactor zones independently comprises a temperature greater than or equal to 100 ° C, and a pressure greater than or equal to 100 MPa.
    [0049] In a process incorporation according to any of the previous incorporations, each of the polymerization conditions in the reactor zones independently comprises a temperature below 400 ° C, and a pressure less than 500 MPa.
    [0050] In a process incorporation according to any of the previous incorporations, the Z1 / Z2 ratio and each Zl / Zi ratio are greater than 1.03.
    [0051] In a process incorporation according to any of the previous incorporations, the Z1 / Z2 ratio and each Zl / Zi ratio are greater than 1.10.
    [0052] In an incorporation of the process according to any of the previous incorporations, the Z1 / Z2 ratio and each Zl / Zi ratio are less than 10.
    [0053] In an incorporation, the inventive process may comprise a combination of two or more incorporations described herein.
    [0054] In an embodiment, the invention is a polymer based on ethylene prepared by the process according to any of the previous embodiments.
    [0055] In an embodiment, the ethylene-based polymer is a polyethylene homopolymer.
    [0056] In an embodiment, the ethylene-based polymer is an ethylene-based interpolymer.
    [0057] In an embodiment, the ethylene-based polymer is an ethylene-based copolymer.
    [0058] In an embodiment, the invention is an ethylene-based polymer having (A) a melt elasticity, in centiNewton, less than or equal to (7.0x (melting index) -0'55) and greater than or equal to (6.0 x (melt index) -0'55) for a polymer with a melt index greater than 0.45 and less than 0.70; or (B) a melt elasticity, in centiNewton, less than or equal to (5.5x (melting index) -0.83) and greater than or equal to (4.0x (melting index) -0.83) for a melt index greater than 2.5 and less than 4.0.
    [0059] In an embodiment, the ethylene-based polymer according to any of the previous embodiments has (1) a melt elasticity, in centiNewton, less than or equal to (6.8 x (melt index) -0.55 ) for a polymer with a melt index greater than 0.45 and less than 0.70; or (2) a melt elasticity, in centiNewton, less than or equal to (5.2 x (melt index) -0.83) for a melt index greater than 2.5 and less than 4.0.
    [0060] In an embodiment, the ethylene-based polymer according to any of the previous embodiments has a density of 0.926 to 0.94 g / cm3, and a melting index of 0.2 to 5 g / 10 min.
    [0061] In an embodiment, the ethylene-based polymer is a polyethylene homopolymer.
    [0062] In an embodiment, the ethylene-based polymer is an ethylene-based interpolymer.
    [0063] In an embodiment, the ethylene-based polymer is an ethylene-based copolymer.
    [0064] In an embodiment, an inventive polymer may comprise a combination of two or more embodiments described herein.
    [0065] In an embodiment, the invention is a composition comprising the ethylene-based polymer according to any of the foregoing polymer embodiments.
    [0066] In an embodiment, the composition comprises yet another ethylene-based polymer.
    [0067] In an embodiment, the inventive composition may comprise the combination of two or more embodiments described herein.
    [0068] In an embodiment, the invention is an article comprising at least one component formed by a composition according to any of the previous composition embodiments.
    [0069] In an incorporation, an inventive article may comprise the combination of two or more incorporations described herein.
    [0070] In an embodiment, the invention is a film comprising at least one component formed by a composition according to any of the previous composition embodiments.
    [0071] In an incorporation, an inventive film may comprise the combination of two or more incorporations described herein. Polymerizations
    [0072] For a polymerization process initiated by free radicals at high pressure, two basic types of reactors are known. 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, the tube having two 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 carried out in an autoclave reactor having at least 2 reaction zones or in a combination of an autoclave and a tubular reactor.
    [0073] In each autoclave zone and in each tubular reactor zone of the process, the temperature is typically from 100 to 400, more typically from 150 to 350 and even more typically from 160 to 320 ° C. In each autoclave zone and in each tubular reactor zone in the process, the pressure is typically 100 to 400, more typically 120 to 360 and even more typically 150 to 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, incorporated in the polymer. The higher the reaction pressure, the more units derived from chain transfer agent will be incorporated into the product.
    [0074] 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 initiator and / or monomer. Appropriate, but not limiting, reactor lengths can be 500 and 1500 meters. Normally, the autoclave reactor has several injection points for initiator and / or comonomer. The particular combination of reactors used allows conversion rates above 20 percent, which are significantly higher than the conversion rates obtained by standard tubular reactors, which allow conversion rates of around 16-18 percent, expressed as ethylene conversion , for the production of low density polymers.
    [0075] Examples of suitable reactor systems are described in USP 3,913,698 and USP 6,407,191. Monomer and comonomers
    [0076] When used in the present description and in the claims, the term ethylene copolymer refers to polymers of ethylene and one or more comonomers. Suitable comonomers to be used in the ethylene polymers of the present invention include, but are not limited to, ethylenically unsaturated monomers and especially C3-20z alpha olefins, acetylenic compounds, conjugated and unconjugated dienes, polyenes, carbon monoxide, vinyl acetate , and C2-6 alkyl acrylates • Initiators
    [0077] 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 commonly used in such processes are: oxygen, which is usable in tubular reactors in conventional amounts between 0.0001 and 0.005 weight percent (weight percent) based on 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 azo dicarboxylic esters, azo dicarboxylic dinitriles and derivatives of 1,2,2,2-tetramethyl ethane. These peroxy organic initiators are used in conventional amounts between 0.005 and 0.2% by weight based on the weight of polymerizable monomers. Chain transfer agents (CTA)
    [0078] Chain transfer agents or telogens are used to control the melt flow rate in a polymerization process. Chain transfer involves terminating growing polymer chains, thus limiting the final molecular weight of the polymeric material. Typically, chain transfer agents are hydrogen atom donors that will react with an increasing 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 selected chain transfer agent, one can control the length of the polymeric chains, and hence the weight average molecular weight, Mw. The melt flow index (MFI or I2) of a polymer, which relates to Mw, is controlled in the same way.
    [0079] The chain transfer agents used in the process of this invention include, but are not limited to, 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 acetaldehyde; and alcohols of saturated aliphatic aldehydes such as methanol, ethanol, propanol or butanol. Preferred chain transfer agents are those with a chain transfer constant (Cs) of at least 0.003 (eg, propane, isobutanol), more preferably at least 0.01 (eg, propylene, isopropanol, acetone, 1-butene), and even more preferably at least 0.05 (for example, methyl ethyl ketone (MEK), propanal (propanoic aldehyde), terciobutanethiol). Cs are calculated as described by Mortimer at 130 ° C and 1360 atm (ref. No. 1-3). Typically, the maximum value of Cs does not exceed 25, more typically it does not exceed 21.
    [0080] In an embodiment, the amount of chain transfer agent used in the process of the present invention is 0.03 to 2.0 weight percent, preferably 0.5 to 1.5 weight percent, based on in the amount of monomer introduced into the reactor system.
    [0081] The manner and timing of the introduction of CTA into the process can vary widely as long as CTA and / or ethylene are recently injected into at least two reaction zones. Typically, the CTA is fed in the first reaction zone together with ethylene and other reaction components, for example, comonomers, initiator, additives, etc., and formation CTA, that is, replacement of the CTA for the CTA consumed in the first zone reactor, it is fed to a reaction reaction zone (2a, 3a, 4a, etc.) downstream. The first reaction zone is an autoclave.
    [0082] In an incorporation, formation CTA is fed together with new ethylene through direct injection and / or together with the injected peroxide solution.
    [0083] In an additional (new) ethylene incorporation without CTA it is fed as a formation flow for ethylene consumed in the first reaction zone or in the first autoclave reaction zone and / or in one or more reaction zones downstream.
    [0084] In an incorporation, the formation CTA is a CTA with a Cs greater than the Cs of the CTA fed in the first reaction zone. This can increase the level of conversion in the reactor system.
    [0085] In an incorporation, the CTA comprises a monomeric group such as propylene, butene-1, etc. The monomeric group improves reactor conversion (it increases comonomer consumption).
    [0086] In an incorporation, the CTA and / or operational conditions in the recycling sections are selected such that the CTA will condense and / or separate from the resulting polymer product in less recycled CTA back to the reactor inlet.
    [0087] In an incorporation, the CTA is purged from the reactor system in a reaction zone downstream.
    [0088] In an incorporation, the reactor system comprises two autoclave reaction zones followed by two tubular reaction zones, and ethylene monomer and CTA are fed in both autoclave reaction zones, but not in any of the tubular reaction zones .
    [0089] In an incorporation, 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 of the tubular reaction zones , but the initiator is fed into one or both tubular reaction zones. Polymers
    [0090] Ethylene-based polymers prepared according to the process of this invention can range from film grade resins, with a very narrow molecular weight distribution (MWD), to coating type resins having much broader MWDE, improving production in the tube or in the autoclave where a smaller or greater degree of counter-mixing is required. Po 1 by immersing ethylene, and optionally comonomers, in an autoclave reactor, a polymeric product having a wide molecular weight distribution will be obtained, whereas polymerization in a tubular reactor will give a polymeric product having a narrow molecular weight distribution. However, surprisingly, using combinations of tubular reactors and autoclave in series, depending on the reaction conditions and percentages of polymerized monomer, it is possible to design polymeric products with very narrow molecular weight distributions. In this way the molecular weight distribution of polyethylene homopolymers or copolymers can be manipulated with more flexibility than a conventional autoclave reactor or in a conventional tubular reactor, while maintaining a high polymer density.
    [0091] Ethylene-based polymers prepared according to this invention have the conversion advantages mentioned above. This distinguishes them from other ways of preparing similar ethylene polymers, occurring in a tubular process. In one aspect, the polymer of this invention has a narrower MWD than that of other polymers prepared in similar reactors that do not use the split CTA concept (Zl / Zi = 1). This is exemplified and quantified with the melt elasticity / melt index, which is a sensitive method for showing these differences as shown in the examples and comparative examples. This is also exemplified by the improvement of the optical film properties associated with narrow MWD.
    [0092] In an embodiment, the ethylene-based polymers of this invention have a typical density of 0.910 to 0.940, more typically from 0.915 to 0.940 and even more typically from 0.926 to 0.940 g / cm3. In one embodiment, the ethylene-based polymers of this invention have a typical melting index (I2) of 0.1 to 100, more typically of 0.12 to 20 and even more typically of 0.15 to 5 g / 10 min at 190 ° C / 2.16 kg. In one embodiment, the ethylene-based polymers of this invention have a typical Mw / Mn (MWD) of 4 to 20, or 5 to 10, or 5 to 6. In one embodiment, the ethylene-based polymers of this invention have a melt elasticity of 1 to 10, typically 2-8 cN (centiNewton). In one embodiment, the ethylene-based polymers of this invention have one or more of these properties of density, melt index, Mw / Mn and melt elasticity.
    [0093] Ethylene-based polymers include LDPE homopolymers (preferred), and high-pressure copolymers include ethylene / vinyl acetate (EVA), ethylene / ethyl acrylate (EEA), and ethylene / butyl acrylate copolymers (EBA). Product applications include shrink bonding film, label film, expanded or cast film for both medium density LDPE (> 0.926 g / cm3) and standard density LDPE (<0.926 g / cm3). Mixtures
    [0094] The inventive polymers may be mixed with one or more polymers, such as, but not limited to, linear low density polyethylene (LLDPE), ethylene copolymers with one or more alpha-olefins such as, but not limited to a, propylene, butene-1, pentene-1,4,4-methyl-pentene-1, hexene-1 and octene-1; high density polyethylene (HDPE) such as HDPE of HD 940-970 grades obtainable from The Dow Chemical Company. The amount of inventive polymer in the mixture can vary widely, but typically it is 10 to 90, 50 to 90, or 70 to 90% 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 constitute the majority of the mixture, that is, it will be rich in LDPE, and will contain an amount greater than or equal to 50% by weight of the inventive polymer, based on the weight of the polymers in the mixture. If the inventive polymer has a relatively large MWD (for example, greater than or equal to 6) then the inventive polymer will constitute the smallest part of the mixture, that is, it will be low in LDPE, and will contain less than 50% by weight of the mixture. inventive polymer, based on the weight of the polymers in the mixture. Mixtures rich in mixed LDPE typically provide good optical properties, and / or are useful in preparing laminates. LDPE-poor mixtures typically exhibit good processability, and / or are useful in applications such as film expansion and extrusion coating. Additions
    [0095] 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, mesh or steel wire , and nylon or polyester strands, nanoparticles, clays, 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
    [0096] 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 film layer, such as a single layer film, or at least one layer in a film multilayer prepared by casting, blowing, calendering or extrusion processes; molded articles, such as blow-molded, injection-molded, or rotational molded articles; extrusions; fibers; and woven or 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 (extenders), crosslinkers, blowing agents, and plasticizers.
    [0097] 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 staple textile fibers, tow, multi-component fibers, core / film, twisted and monofilament. Appropriate fiber forming processes include spin-bonded, melt blown techniques disclosed in USP 4,340,563 (Appel, et al.), USP 4,663,220 (Wisneski, et al.), USP 4,668,566 (Nohr, et al. ), and USP 4,322,027 (Reba), gel-spun 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 up of such fibers , including mixtures with other fibers, such as polyester, nylon or cotton, thermoformed articles, extruded profiles, including extrusions and coextrusions of profiles, calendered articles, and stretched, twisted or crimped fibers or yarns.
    [0098] The inventive polymer can be used in a variety of films including, but not limited to, shrink films, bonding shrink films, stretched hollow films, silage films, stretched covers, sealants, and diaper liners. Films prepared with the inventive polymer often exhibit desirable optical properties, for example, an opacity index less than 15, 12 or 10 percent and / or a gloss index greater than 46, 52, or 56%. In one embodiment, a film made with the polymer of this invention exhibits an opacity index less than 15, 12 or 10 percent and / or a gloss index greater than 46, 52 or 56%.
    [0099] 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 in 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.
    [00100] Other applications suitable for the inventive polymer include fibers and elastic films; soft-touch products, such as toothbrush handles and appliance handles; gaskets and profiles; adhesives (including hot melt 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; cap liners, flooring; and viscosity modifiers, also known as pour point modifiers, for lubricants.
    [00101] Additional treatment of the polymer of this invention can be performed for applications in other end uses. For example, dispersions (both aqueous and non-aqueous) can also be formed using the present polymers or formulations comprising them. Cured foams comprising the inventive polymer can also be formed, as disclosed in PCT publication No. 2005/021622 (Strabdeburg, et al.). The inventive polymer can also be cross-linked by any known means, such as the use of peroxide, electronic beam, silane, azide, or other cross-linking technique. The inventive polymer can also be modified chemically, such as grafting (for example, by using maleic anhydride (MAE), silanes, or other grafting agent), halogenation, amination, sulfonation, or other chemical modification.
    [00102] In an embodiment, the polymers of this invention and those of PCT / US10 / 60244 are used in the construction of release liners for use with the production of pressure sensitive adhesive labels (PSA). Each advanced design of the resins prepared by these inventions satisfies extrusion or film coating performance in combination with higher temperature resistance which is a result of higher product density. Medium density polymers disclosed in PCT / US10 / 60244 are especially suitable for extrusion coatings and release liners. The polymers of the present invention are especially suitable for single or multilayer films.
    [00103] In some incorporations, release liners are prepared by a two-step process. The first step consists of coating paper with a polyolefin resin, for example, a polyethylene such as LDPE. The second step consists of coating and drying the polyolefin-coated paper with a layer of silicone. Thus, polyolefinic resin has to comply with several requirements, that is, it must exhibit extrusion coating stability, adhesion to paper, and temperature resistance in the drying oven for siliconization. High density polymers (0.926 to 0.935 g / cm3) show improved temperature resistance for the second drying / siliconization step in an extrusion coating application. In addition, the LDPE prepared by the process of this invention has the cleaning required for silicone systems containing high platinum catalyst. Definitions
    [00104] Unless stated otherwise, 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 this disclosure. 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 disclosure of definitions (to the extent not inconsistent with any definitions provided herein) and general knowledge in the art.
    [00105] The numerical ranges in this disclosure are approximate, and therefore may include values outside the range unless otherwise indicated. The numerical ranges include all values from the lower to the upper value, in increments of one unit, provided that there is a separation of at least two units between any lower value and any higher value. As an example, if it is stated that the quantity of a component, or a value of a composition or physical property, such as, for example, quantity of a mixing component, softening temperature, melting index, etc., is between 100 and 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 in this report. For ranges containing values that are less than one, or containing fractional numbers greater than one (for example, 1.1, 1.5, etc.) a unit is considered to be 0.0001, 0.001, 0.01 or 0.1, when appropriate. For ranges containing single digit numbers less than ten (for example, 1 to 5), a unit is typically considered to be 0.1. These are just examples of what is specifically intended, and all possible combinations of numerical values between the minimum and maximum values listed will be considered to be expressly stated in this patent application. Within this disclosure, numerical ranges are provided for, among other things, density, melt index, molecular weight, quantities of reagents and process conditions.
    [00106] 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 in combination with at least one other material, for example, an additive, filler, another polymer, catalyst, etc.
    [00107] When used herein, the term "mixture" or "polymeric mixture" means an intimate physical mixture (that is, without reaction) of two or more polymers. Such a mixture may or may not be miscible. Such a mixture may or may not be separated by phases. Such a mixture may or may not contain one or more domain configurations, determined from electronic transmission spectroscopy, light scattering, X-ray scattering, and any other method known in the art. The mixture can be prepared by physically mixing two or more polymers at the macro level (for example, melt mix composition or resins) or at the micro level (for example, simultaneous formation within the same reactor).
    [00108] The term "polymer" refers to a compound prepared by reacting monomers of the same or different types. Therefore, the generic term "polymer" includes 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.
    [00109] The term "interpolymer" refers to polymers prepared by the polymerization of at least two different types of monomers. Therefore, the generic term interpolymer includes copolymers (which refer to polymers prepared from two different types of monomers), and polymers prepared from more than two different types of monomers.
    [00110] The term "ethylene-based polymer" or "ethylene polymer" refers to a polymer comprising a majority amount of polymerized ethylene, based on the weight of the polymer, and optionally, can comprise at least one comonomer.
    [00111] 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 polymer, and comprises at least one comonomer.
    [00112] The term "reaction zone" refers to a section of a reactor where a polymerization reaction occurs via free radicals, injecting an initiator system, which is capable of decomposing the radicals under conditions within the zone. A reaction zone can be a separate reactor unit or 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 deflector, preventing counter-mixing. Each reactor zone has its own initiator feed, while feeds of ethylene, comonomer, chain transfer agent and other components can be transferred from a previous reaction zone, and / or recently injected (as separate or mixed components) .
    [00113] 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, existing dead polymer molecules can be restarted, resulting in the formation of long chain branches (LCB) in the original polymeric (linear) 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.
    [00114] The term "polymerization conditions" refers to the process parameters under which the initiator entering the 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, influencing the molecular weight distribution and the polymeric structure. The influence of polymerization conditions on the polymeric product is well described and modeled in S. Goto et al., Ref. N ° 1.
    [00115] 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 polymeric molecule containing a radical by which the radical is transferred to the CTA molecule, which can then initiate a new polymeric chain. CTA is also known as a telogen or telomer. In a preferred embodiment of the invention, each CTA system comprises a single CTA.
    [00116] The term "suction for a hyper compressor" refers to the final compressor before the reactor that conducts one or more feed streams to the reactor pressure of a lower pressure. The suction for a hyper compressor is the input configuration of this compressor.
    [00117] The term "discharge of hyper compressor" refers to the output configuration of the hyper compressor. Testing methods Polymer testing methods
    [00118] Density: 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 2 07 MPa for 1 minute. Measurements are performed within one hour of pressing the sample using Method B of ASTM D 792.
    [00119] melting index: Measuring melting index, or I2, (g / 10 min) according to ASTM D 1238, Condition 190 ° C / 2.16 kg. Measure 10 according to ASTM D 1238, Condition 190 ° C / 10 kg.
    [00120] Melt elasticity: Melt elasticity is measured using the DMELT system. The DMELT system comprises a commercial plastomer, a digital scale incorporating a heavy sample pan for use mounted with a tensioning cylinder, and a traction cylinder controlled by a step motor. The plastomer produces a row of molten polymer that is guided around the tensioning cylinder over the scale pan and up to another upper pulley before being wound onto the tension cylinder. The speed of the traction cylinder is precisely controlled by computer. The melt elasticity is determined as the force on the tension roller at a specified stretch ratio (drag speed / die exit speed). The technology is applicable to thermoplastic and / or thermoset plastics.
    [00121] For the measurement of melt elasticity, a row of melted polymer is extruded from a standard plastomer cylinder (MP600 Extrusion Plastomer (Melt Indexer) System Installation & Operation Manual (# 020011560), Tinius Olsen, 1065 Easton Road, Horsham, PA 19044-8009; Ref. No. 13.6) at a constant temperature (190 ° C) through a standard MFR matrix of ASTM D 1238 (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 onto a cylinder driven by a stepper motor (Stepper Motor and Controller Operating Manual, Oriental Motor USA Corporation, 2570 W. 237thStreet, Torrance, CA 90505; Ref. N ° 13.7 ) which has its velocity staggered over a range of speeds during the analysis. The polymer extraction force is registered on the tensioning cylinder mounted on the scale platform (Excellence Plus XP Precision Operating Instructions, Mettler Toledo, 1900 Polaris Parkway, Columbus, Ohio 43240; Ref. 13.8) by the integrated control computer. From a linear regression of the acquired force data, the final recorded 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 the matrix output speed. The analysis results are given in centiNewton (cN).
    [00122] Gel permeation chromatography with 3 detectors: GPC analysis with 3 detectors is performed on a GPCV2000 Alliance instrument (Waters Corp.) adjusted to 145 ° C. The flow rate for GPC is 1 mL / min. The injection volume is 218.5 pL. The column set consists of four Mixed-A columns (20 pm particles; 7.5 x 300 mm; Polymer Laboratories Ltd.).
    [00123] Detection is achieved using a PolymerChar IR4 detector, equipped with a CH sensor; a Wyatt Technology Dawn HALS DSP detector (Wyatt Technology Corp., Santa Barbara, CA, USA), equipped with a 30 mW argon / ion laser operating at X = 488 nm; and a Waters three capillary viscosity detector. The HALS 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 a polydispersion of 1.11. A specific refractive index (dn / dc) increment of 0.104 mL / mg is used for polyethylene in TCB.
    [00124] Conventional GPC calibration is done with 20 narrow polystyrene (PS) standards (Polymer Laboratories Ltd.) with molecular weights in the range of 580-7,500,000 g / mol. The maximum molecular weights of the polystyrene standards are converted to molecular weights of polyethylene using the equation Mpolethylene = AX (Mpolystyrene) B With A = 0.39, B = 1. The value of A is determined using HDPE Dow 53494-38- 4, a linear polyethylene homopolymer with 115,000 g / mol Mw. 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.
    [00125] For sample preparation, as well as for the GPC experiments of 3 detectors, the 1,2,4-trichlorobenzene distilled of "Baker analysis" grade (JT Baker, Deventer, Netherlands) containing 200 ppm 2,6-ditherciobutyl-4-methyl phenol (Merck, Hohenbrunn, Germany). HDPE SEM 1483 is obtained from the U.S. National Institute of Standards and Technology (Gaithersburg, MD, USA).
    [00126] LDPE solutions are prepared by dissolving the samples with gentle agitation for three hours at 160 ° C. PS standards are dissolved in the same conditions for 30 minutes. The sample concentration for the 3-detector GPC experiments is 1.5 mg / mL and the polystyrene concentration is 0.2 mg / mL.
    [00127] The MALS detector measures the scattered signal of the polymers or particles in a sample at different scattering angles θ. The basic light scattering equation (by M. Andersson, B. Wittgren, GG Wahlung, Anal. Chem. 75, 4279 (2003)) can be written as
    where Rθ is the Rayleigh ratio of excess, K is an optical constant, which, among other things, depends on the increment of specific refractive index (dn / dc), c is the concentration of the solute, M is the molecular weight, Rg is the radius of rotation, and À 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 plotting (Kc / Rθ) 1/2 as a function of sen2 (θ / 2) on the so-called Debye graph. The molecular weight can be calculated from the intercept with the ordinate, and the radius of rotation of the initial slope of the curve. Zimm and Berry methods are used for all data. The second virial coefficient is considered negligible. The intrinsic viscosity numbers of both the concentration detector signals and the viscosity detector signals are calculated considering the ratio of the specific viscosity and the concentration in each elution slice.
    [00128] ASTRA 4.72 software (Wyatt Technology Corp.) is used to collect the signals from the IR detector, viscometer, and MALS detector. Data processing is done with Microsoft EXCEL macros written in the company.
    [00129] The calculated molecular weights and molecular weight distributions are obtained using a light scattering constant derived from one or more of the mentioned polyethylene standards and a refractive index concentration coefficient, dn / dc, of 0.104. Generally, mass detector response and light scattering constant should be determined from a linear pattern with a molecular weight in excess of about 50,000 Dalton. Viscometer calibration can be performed using the methods described by the manufacturer or, alternatively, using the published values of appropriate linear standards such as Standard Reference Materials (SEM) 1475a, 1482a, 1483, or 1484a. It is assumed that the chromatographic concentrations are low enough to eliminate the effects of the 2nd virial coefficient of addressing (effects of concentration on molecular weight).
    [00130] Dynamic mechanical spectroscopy (DMS): Compression molds the resin on a rectangular plate 70 mm x 100 mm x 2 mm thick at 159 ° C for 3 minutes at a pressure of 1 MPa, followed by 1 minute at pressure of 15 MPa. Then, the sample is taken from the press and cooled quickly to room temperature.
    [00131] Molten rheology and constant temperature frequency scans are performed using an "Advanced Rheometric Expansion System (ARES)" from TA Instruments equipped with parallel 25 mm plates, under nitrogen purge. The sample is placed on a plate and allowed to melt for 5 minutes at 190 ° C. The plates are then brought to 2 mm, the sample equalized, and then the test is started. The method has an additional delay of five minutes built in, to allow temperature equilibrium. The experiments are carried out at 150 ° C over a frequency range of 0.1 to 100 rad / s. The strain range is constant at 10%. The voltage response is analyzed in terms of amplitude and phase, from which the storage module (G '), the loss module (G "), the dynamic viscosity η *, and the tangent (tg) ( δ). Film test conditions
    [00132] Opacity: Samples measured for overall opacity are obtained and prepared according to ASTM D 1003. The films were prepared as described in the experimental section below.
    [00133] 45 ° brightness: 45 ° brightness is measured by ASTM d- 2457. The films were prepared as described in the experimental section below. Experimental Zl, Z2 and Zi calculations:
    [00134] The "molar concentration of reactor zone of a CTA j in a reactor zone i ([CTA] ji)" is defined as the "total molar quantity of that CTA recently injected in reactor zones 1 ai" divided by "quantity total molar of ethylene recently injected in the reactor zones 1 ai ".
    [00135] This relationship is shown below in Equation A.

    [00136] In Equation A, j> 1, nCTA (j is the "quantity of moles of the jth CTA recently injected in the i-th reactor zone" and neth is the "quantity of moles of ethylene recently injected in the i- th reactor zone ".
    [00137] The "transfer activity of a CTA (system) in a reactor zone i" is defined as the "sum of the molar concentrations of each CTA in the reactor zone" multiplied by its chain transfer activity constant (Cs) . The chain transfer activity constant (Cs), the ratio of reaction rates Ks / Kp, at a reference pressure (1360 atm) and a reference temperature (130 ° C). This relationship is shown below in Equation B, where nCOmp, i is the total number of CTAs in reaction zone i. n comp, 1.

    [00138] Consequently, the Zl / Zi ratio is shown below in Equation C.

    [00139] The chain transfer constant values (Cs) for some chain transfer agents are shown below in Table B, showing Mortimer-derived chain transfer constants (Cs) at 130 ° C and 1360 atm for examples of chain transfer agents. Table B. Values of Cs measured by Mortimer at 130 ° C and 1360 atm in references 3 and 4
    Ref. No. 2. G.Mortimer; Journal of Polymer Science: Part A; Chain transfer in ethylene polymerization; vol. 4, p 881-900 (1966). Ref. No. 3. G.Mortimer; Journal of Polymer Science: Part A; Chain transfer in ethylene polymerization. Part IV. Additional Study at 1360 atm and 130 ° C; vol. 8, p 1513-1523 (1970). Ref. No. 4. G.Mortimer; Journal of Polymer Science: Part A; Chain transfer in ethylene polymerization. Part VII. Very reactive and depletable transfer agents; vol. 10, p 163-168 (1972).
    [00140] When using only one CTA in the total reactor system, Equations B and C are simplified in Equations D and E, respectively.

    [00141] For five of the six polymerizations (three inventive, two comparative) discussed below, only one CTA was used. For one of the comparative polymerizations, two CTAs were used as the CTA system. Four reactor zones configured as AAT T. are used. Reactor zone 1 is A, reactor zone 2 is A, reactor zone 3 is T, reactor zone 4 is T. CTA is injected into the zones 1 and 2, only initiator is injected in zones 3 and 4, however, typically some CTA is transported from zones 1 and 2 to zones 3 and 4. No CTA is added in reactor zones 3 and 4.
    [00142] Only one CTA implies that Cs falls out of equations, and therefore Equation E is used in most examples, as shown below.

    [00143] In addition, the tubular part of the AC reactor / tube system (which is the system used to generate all the examples) can be considered as reactor zones 3 and 4, where both zones do not receive any CTA or additional injected ethylene recently. This means that Equation E becomes as shown below. Thus, Zl / Z4 = Zi / Z3— Z1 / Z2.

    [00144] Furthermore, for all examples: nθth i-neth 2r and therefore, the relationship is further simplified as shown below.
    Polymerization and polymers
    [00145] Comparative Example 1: The MEK (CTA) formed is equally divided by both autoclave reaction zones d and 2) Reactor pressure: 2440 bar. Autoclave time (AC): 55 seconds. Dwell time in tubular: 80 seconds.
    [00146] Tertiobutyl peroxy perpivalate (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 terciobutyl peroxide (DTBP) is injected as an additional free radical initiator. Temperature conditions:
    [00147] Autoclave top zone (50% ethylene): Input: 37 ° C; control 171 ° C.
    [00148] Autoclave bottom zone (50% ethylene): Input: 35 ° C; control 171 ° C.
    [00149] Control of 1st tube zone: 271 ° C.
    [00150] Control of 2nd tube zone: 271 ° C.
    [00151] Methyl ethyl ketone (MEK) is used as the chain transfer agent. Recycled MEK (after partial conversion in the reactor, partial condensation in the low pressure recycling section and / or partial purge) is equally divided by both reactor ethylene feed streams and both AC reaction zones. The newly formed MEK (to maintain MEK concentration in order to control / vary MI) is equally divided by both AC reaction zones.
    [00152] For this polymerization, for the average sample
    Product sampling
    [00153] Samples are taken to measure the results of the polymer rheology the average sample (ld) is taken for evaluation of expanded film. Table 1 shows the results. Table 1: Comparative Examples la-ld. Results of rheology and MEK concentrations.

    [00154] * Samples la-lc are samples of actual final polymerization. Sample ld represents the average of samples lc.
    [00155] Inventive Example 2: MEK (CTA) formed is sent to the autoclave top reaction zone. Reactor pressure: 2440 bar.
    [00156] Autoclave time (AC): 55 seconds.
    [00157] Dwell time in tubular: 80 seconds.
    [00158] Inject tert-butyl peroxy perpivalate (TBPV) 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 terciobutyl peroxide (DTBP) is injected as an additional free radical initiator. Temperature conditions: Autoclave top zone (50% ethylene): Input: 37 ° C; control 171 ° C. Autoclave bottom zone (50% ethylene): Input: 35 ° C; control 171 ° C. Control of 1st tube zone: 259 ° C. 2nd tube zone control: 258 ° C.
    [00159] Methyl ethyl ketone (MEK) is used as the chain transfer agent. Recycled MEK (after partial conversion in the reactor, partial condensation in the low pressure recycling section and / or partial purge) is equally divided by both reactor ethylene feed streams and both AC reaction zones. The newly formed MEK (to maintain MEK concentration in order to control MI) is fed into the ethylene feed stream sent to the autoclave top zone.
    [00160] For this polymerization, for the average sample:
    Product sampling
    [00161] Samples are taken to measure the polymer rheology response, and the average sample (2e) is taken for expanded film evaluation. Table 2 shows the results. Table 2: Example 2. Results of rheology and MEK concentrations.

    [00162] * Samples 2a-2d are samples of actual final polymerization. Sample 2e represents the average of samples 2a-2d.
    [00163] Comparative Example 3: The MEK (CTA) formed is equally divided by both autoclave reaction zones (1 and 2) Reactor pressure: 2440 bar. Autoclave time: 55 seconds. Dwell time in tubular: 80 seconds.
    [00164] Tertiobutyl peroxy perpivalate (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 terciobutyl peroxide (DTBP) is injected as an additional free radical initiator. Temperature conditions: Autoclave top zone (50% ethylene): Input: 43 ° C; control 171 ° C. Autoclave bottom zone (50% ethylene): Input: 40 ° C; control 171 ° C. Control of 1st tube zone: 272 ° C. 2nd tube zone control: 271 ° C.
    [00165] Methyl ethyl ketone (MEK) is used as the chain transfer agent. Recycled MEK (after partial conversion in the reactor, partial condensation in the low pressure recycling section and / or partial purge) is equally divided by both reactor ethylene feed streams and both AC reaction zones. The newly formed MEK (to maintain MEK concentration in order to control / vary MI) is equally divided by both AC reaction zones. In addition, a low level (0.7% by volume) of propylene in the reactor supply is maintained to control product density.
    [00166] For this polymerization, for the average sample:
    Product sampling
    [00167] Samples are taken to measure the polymer rheology response the average sample (3d) is taken for evaluation of expanded film. Table 3 shows the results. Table 3: Comparative Examples 3. Results of rheology and MEK concentrations.
    * Samples 3a-3c are samples of actual final polymerization. Sample 3d represents the average of samples 3a-3c. Inventive Example 4: MEK (CTA) formed is sent to the autoclave top reaction zone. Reactor pressure: 2440 bar. Autoclave time (AC): 55 seconds. Dwell time in tubular: 80 seconds.
    [00168] Tertiobutyl peroxy perpivalate (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 terciobutyl peroxide (DTBP) is injected as an additional free radical initiator. Temperature conditions: Autoclave top zone (50% ethylene): Input: 43 ° C; control 171 ° C. Autoclave bottom zone (50% ethylene): Input: 40 ° C; control 171 ° C. Control of 1st tube zone: 273 ° C. 2nd tube zone control: 271 ° C.
    [00169] Methyl ethyl ketone (MEK) is used as the chain transfer agent. Recycled MEK (after partial conversion in the reactor, partial condensation in the low pressure recycling section and / or partial purge) is equally divided by both reactor ethylene feed streams and both AC reaction zones. The newly formed MEK (to maintain MEK concentration in order to control MI) is fed into the ethylene feed stream sent to the autoclave top zone. No propylene is added and no propylene is present in the reactor feeds. For this polymerization, for the average sample
    Product sampling:
    [00170] Samples are taken to measure the rheology response of the polymer, and the average sample (4d) is taken for evaluation of expanded film. Table 4 shows the results. Table 4: Example 4a-4d. Results of rheology and MEK concentrations.
    * Samples 4a-4c are samples of actual final polymerization. Sample 4d represents the average of samples 4a-4c. Comparative Example 5: The formed propylene (CTA) is equally divided by both autoclave reaction zones (1 and 2) Reactor pressure: 2000 bar. Autoclave time (AC): 55 seconds. Dwell time in tubular: 80 seconds.
    [00171] Inject tert-butyl peroxy perpivalate (TBPV) 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 terciobutyl peroxide (DTBP) is injected as an additional free radical initiator. Temperature conditions: Autoclave top zone (50% ethylene): Input: 40 ° C; control 202 ° C. Autoclave bottom zone (50% ethylene): Input: 36 ° C; control 236 ° C. Control of 1st tube zone: 275 ° C. 2nd tube zone control: 275 ° C.
    [00172] Propylene is used as the 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 between both reactor ethylene feed streams and both AC reaction zones. The newly formed propylene (to maintain propylene concentration in order to control / vary MI) is equally divided by both AC reaction zones. Product sampling
    [00173] Samples are taken to measure the rheology response and for evaluation of expanded film. Table 5 shows the results. Table 5: Comparative Example 5. Results of rheology and MEK concentrations.

    [00174] Inventive Example 6: The formed propylene (CTA) is equally divided by both autoclave reaction zones d and 2) Reactor pressure: 2000 bar. Autoclave time: 55 seconds. Dwell time in tubular: 80 seconds.
    [00175] Tertiobutyl peroxy perpivalate (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 terciobutyl peroxide (DTBP) is injected as an additional free radical initiator. Temperature conditions: Autoclave top zone (50% ethylene): Input: 40 ° C; control 203 ° C. Autoclave bottom zone (50% ethylene): Input: 36 ° C; control 236 ° C. Control of 1st tube zone: 275 ° C. 2nd tube zone control: 275 ° C.
    [00176] Propylene is used as the 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 between both reactor ethylene feed streams and both AC reaction zones. The newly formed propylene (to maintain propylene concentration in order to control MI) is equally divided by both AC reaction zones. Product sampling
    [00177] Samples are taken to measure the rheology response and to evaluate expanded film. Table 6 shows the results. Table 6: Example 6. Results of rheology and MEK concentrations.
    improved pseudoplasticity index (ESTI)
    [00178] The improved pseudoplasticity index (ESTI) is a measure of DMS (dynamic-mechanical spectrometry, also known as oscillatory shear rheology, described above), derived from two commonly measured variables that capture MWD amplitude or narrowness of LDPEs, eliminating the dominant effect of fusion index. All that is needed is a single frequency scan from 0.1 rad / s to 100 rad / s at 190 ° C. ESTI is defined as:
    where | η * (w) | is the magnitude of the complex viscosity at frequency w.
    [00179] Comparative Examples and Inventive Examples 1- 4 show a satisfactory agreement between the width of MWD examined by ESTI and the width of MWD examined by MIME. The ESTI of Comparative Example 5 and Inventive Example 6 also show this effect closely as seen in Figure 6. Table 7. Properties of the example polymers.
    Polymers and films
    [00180] Each of the films was molded using the process parameters shown in Table 8. The inventive film 1 was made from a sample of the polymer (density of 0.930 g / cm3) prepared in Example 2 best represented by sample 2e in terms of its polymer rheology characteristics (MI, ME and ESTI). The inventive film 2 was made from a sample of the polymer (density of 0.929 g / cm3) prepared in Example 4 best represented by sample 4d in terms of its polymer rheology characteristics (MI, ME and ESTI)
    [00181] The inventive film 3 was made from a sample of the polymer (density of 0.919 g / cm3) prepared in Example 6.
    [00182] Comparative film 1 was made from a sample of the polymer (density of 0.930 g / cm3) prepared in Comparative Example 1 best represented by sample ld in terms of its polymer rheology characteristics (MI, ME and ESTI) .
    [00183] Comparative film 2 was made from a sample of the polymer (density 0.927 g / cm3) prepared in Comparative Example 3 best represented by the 3d sample in terms of its polymer rheology characteristics (MI, ME and ESTI) .
    [00184] Comparative film 3 was made from a sample of the polymer (density of 0.919 g / cm3) prepared in Comparative Example 5.
    [00185] All films are made with a "25/1 chromium-plated spindle (3/1 compression ratio; 10D feeding zone; 3D transition zone; 12D measurement zone)" connecting a "25 matrix mm in diameter ". No internal bubble cooling is used. Table 8 shows the general expanded film parameters used to produce the film. In all examples and comparative examples the same conditions were used. Drum 1 of the temperature profile is the closest to the pellet loading funnel followed by drum 2, which is followed by drum 3, which is followed by drum 4. A micrometer was used to measure the thickness of the films. Table 8 - Manufacturing conditions for expanded film

    [00186] Tables 9-11 and Figures 3-5 show, respectively, the films and their optical properties. All means and standard deviations are based on measurements per sample. Table 9. Optical properties of expanded film samples from Comparative Example ld and Example 2e.
    Table 10. Optical properties of expanded film samples from Comparative Example 3d and Example 4d.
    Table 11. Optical properties of expanded film samples from Comparative Example 5 and Example 6.

    [00187] The polymers produced here are in three melt index classes: one between MI of 2 and 4 dg / min, one between MI of 0.4 and 0.7 dg / min, and one between MI of 0.9 and 1.1 dg / min. The melt elasticity and the ESTI as a function of melt index are sensitive techniques, and show that a general trend of lower melt elasticity and lower ESTI is obtained from the inventive examples. This is a direct consequence of the CTA arrangement of this invention, leading to a narrower molecular weight distribution. The film measurements under fixed conditions show that this lower melt elasticity translates into better optical properties. The polymers are as narrow as the best products in the LDPE film class, when prepared under advantageous process conditions, mainly higher conversion.
    [00188] Although the invention has been described in certain details through the previous description of the preferred embodiments, these details have the main purpose of illustration. Many variations and modifications can be made by someone 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)
    [0001]
    1. High pressure polymerization process to form an ethylene-based polymer, characterized by the fact that it comprises the steps of: (A) Injecting a first feed comprising a chain transfer agent system (CTA system) and ethylene 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 Zl transfer activity; and (B) (1) Transfer at least part of the first zone reaction product 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 a second new feed comprising a CTA and ethylene system in the second reactor zone to produce a second zone reaction product, with the proviso that the CTA system in the second reactor zone has a Z2 transfer activity; and with the proviso that the ratio of Z1: Z2 is greater than 1.
    [0002]
    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 an (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 reaction having a Zi transfer activity with the proviso that the Zl / Zi ratio is greater than 1.
    [0003]
    3. Process according to claim 1, characterized in that at least part of the reaction product from the first zone is transferred to a second autoclave reactor zone.
    [0004]
    4. Process according to claim 1, characterized in that at least part of the first zone reaction product is transferred to a tubular reactor zone.
    [0005]
    5. Process, according to claim 1, characterized by the fact that each feed for each reactor zone contains the same CTA system.
    [0006]
    6. Process according to claim 1, characterized by the fact that at least one CTA has a Cs chain transfer constant greater than 0.003.
    [0007]
    7. Process according to claim 1, characterized by the fact that each of the polymerization conditions in the reactor zones independently comprises a temperature greater than or equal to 100 ° C, and a pressure greater than or equal to 100 MPa .
    [0008]
    8. Process according to claim 2, characterized by the fact that the Z1 / Z2 ratio and each Zl / Zi ratio are greater than 1.03.
    [0009]
    9. Process, according to claim 2, characterized by the fact that the Z1 / Z2 ratio and each Zl / Zi ratio are less than 10.
    [0010]
    10. Ethylene-based polymer, prepared by the process of claim 1, characterized by the fact that it also comprises a density of 0.926 to 0.94 g / cm3, and a melting index of 0.2 to 5 g / 10 min.
    [0011]
    11. Ethylene-based polymer according to claim 10, characterized in that the polymer is a polyethylene homopolymer.
    [0012]
    12. Ethylene-based polymer according to claim 10, characterized in that the polymer is an ethylene-based interpolymer.
    [0013]
    13. Composition, characterized by the fact that it comprises the ethylene-based polymer as defined in claim 10.
    [0014]
    14. Article, characterized by the fact that it comprises at least one component comprising the ethylene-based polymer as defined in claim 10.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112013007510B1|2020-10-20|high pressure polymerization process to form an ethylene-based polymer, ethylene-based polymer, composition and article
    BR112012015026B1|2019-11-05|high pressure polymerization process to form an ethylene based polymer, ethylene based polymer, composition, article and film
    US9403928B2|2016-08-02|Polymerization process to make low density polyethylene
    BR112016013042B1|2020-12-15|POLYMER BASED ON ETHYLENE, COMPOSITION AND ARTICLE
    BR112014012272B1|2021-01-26|ethylene-based polymer, composition and article
    KR102166723B1|2020-10-20|Compositions containing low density ethylene-based polymers with high melt strength and films formed from the same
    BR112015010787B1|2022-01-18|LOW DENSITY ETHYLENE BASED COMPOSITION, ITEM AND POLYMERIZATION METHOD TO FORM A LOW DENSITY ETHYLENE BASED COMPOSITION
    BR112014009303B1|2021-02-02|high pressure polymerization process
    BRPI0516921B1|2016-04-12|ethylene homopolymer or copolymer and free radical initiation polymerization process
    SK10132000A3|2001-07-10|Homopolymers and copolymers of ethylene
    US20090061135A1|2009-03-05|Polyolefin resin blends for crack-resistant pipe
    BR112015008956B1|2021-07-06|polyethylene composition, its preparation process and manufactured articles comprising it
    BR112015023342B1|2021-08-10|ETHYLENE POLYMER
    BR112012005692B1|2021-07-27|POLYMER COMPRISING A SILOXAN, COMPOSITION AND ARTICLE
    BR112020001030A2|2020-07-14|low-density ethylene-based polymers for low-speed extrusion coating operations
    US11236183B2|2022-02-01|Polyethylene composition having high swell ratio, fnct and impact resistance
    WO2021202349A1|2021-10-07|Substituted silanes as chain transfer agents for polyolefin production
    同族专利:
    公开号 | 公开日
    KR101911673B1|2018-10-24|
    US9534064B2|2017-01-03|
    KR20140009164A|2014-01-22|
    EP2621963A1|2013-08-07|
    AR083077A1|2013-01-30|
    EP2621963B1|2016-07-06|
    JP5980214B2|2016-08-31|
    KR20180049190A|2018-05-10|
    BR112013007510A2|2016-11-08|
    US9234055B2|2016-01-12|
    WO2012044504A1|2012-04-05|
    CN103237819A|2013-08-07|
    ES2592184T3|2016-11-28|
    JP2013543025A|2013-11-28|
    US20130197168A1|2013-08-01|
    CN103237819B|2016-10-26|
    US20160115256A1|2016-04-28|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2964515A|1957-07-01|1960-12-13|Nat Distillers Chem Corp|Ethylene polymerization process|
    US3756996A|1964-10-02|1973-09-04|Nat Distillers Chem Corp|Process for the production of ethylene polymers|
    US3485706A|1968-01-18|1969-12-23|Du Pont|Textile-like patterned nonwoven fabrics and their production|
    US3536693A|1968-01-31|1970-10-27|Eastman Kodak Co|Process for preparing polyethylene having improved properties|
    DE2107945A1|1971-02-19|1972-08-24|F J Gattys Ing Buero F Chem Ma|High pressure polyethylene prodn - using stirred autoclave and tubular after-reactor for high yield and quality|
    US3913698A|1974-02-01|1975-10-21|Power Matic Corp|Variable speed transmission|
    JPS5415905B2|1976-08-13|1979-06-18|
    DE2814650C2|1978-04-05|1984-02-02|EC Erdölchemie GmbH, 5000 Köln|Production of homo- or copolymers of ethylene by the high pressure process in a stirred autoclave with practically complete backmixing|
    US4340563A|1980-05-05|1982-07-20|Kimberly-Clark Corporation|Method for forming nonwoven webs|
    US4322027A|1980-10-02|1982-03-30|Crown Zellerbach Corporation|Filament draw nozzle|
    US4413110A|1981-04-30|1983-11-01|Allied Corporation|High tenacity, high modulus polyethylene and polypropylene fibers and intermediates therefore|
    US4599392A|1983-06-13|1986-07-08|The Dow Chemical Company|Interpolymers of ethylene and unsaturated carboxylic acids|
    US4663220A|1985-07-30|1987-05-05|Kimberly-Clark Corporation|Polyolefin-containing extrudable compositions and methods for their formation into elastomeric products including microfibers|
    US4668566A|1985-10-07|1987-05-26|Kimberly-Clark Corporation|Multilayer nonwoven fabric made with poly-propylene and polyethylene|
    US4988781A|1989-02-27|1991-01-29|The Dow Chemical Company|Process for producing homogeneous modified copolymers of ethylene/alpha-olefin carboxylic acids or esters|
    DE3912975A1|1989-04-20|1990-11-08|Basf Ag|POLYETHYLENE AND COPOLYMERISATES FROM MAJOR CONTENTS OF ETHYLENE|
    DE4132012A1|1991-09-26|1993-04-01|Basf Ag|ETHYLENE HOMOPOLYMERS AND COPOLYMERS AND A METHOD FOR THE PRODUCTION THEREOF|
    CA2232389A1|1995-09-29|1997-04-03|Seema V. Karande|Cross-linked polyolefinic foams and process for their production|
    EP0928797B3|1998-01-12|2012-01-11|Dow Global Technologies LLC|Medium density ethylene polymers, a process to prepare these polymers and use of carbonyl group containing chain transfer agents in this process|
    US6407191B1|1998-01-12|2002-06-18|The Dow Chemical Company|Medium density ethylene polymers, a process to prepare these polymers and use of carbonyl group containing chain transfer agents in this process|
    US7406537B2|2002-11-26|2008-07-29|Progress Software Corporation|Dynamic subscription and message routing on a topic between publishing nodes and subscribing nodes|
    TW200517426A|2003-08-25|2005-06-01|Dow Global Technologies Inc|Aqueous dispersion, its production method, and its use|
    WO2006049783A1|2004-11-02|2006-05-11|Dow Global Technologies Inc.|Process for producing low density polyethylene compositions and polymers produced therefrom|
    KR20110084905A|2008-10-07|2011-07-26|다우 글로벌 테크놀로지스 엘엘씨|High pressure low density polyethylene resins with improved optical properties produced through the use of highly active chain transfer agents|
    ES2555498T3|2009-12-18|2016-01-04|Dow Global Technologies Llc|Polymerization process for manufacturing low density polyethylene|
    IN2014CN02739A|2011-10-19|2015-07-03|Dow Global Technologies Llc|US9150681B2|2010-10-29|2015-10-06|Dow Global Technologies Llc|Ethylene-based polymers and processes for the same|
    IN2014CN02739A|2011-10-19|2015-07-03|Dow Global Technologies Llc|
    US9228036B2|2011-11-23|2016-01-05|Dow Global Technologies Llc|Low density ethylene-based polymers with broad molecular weight distributions and low extractables|
    BR112014012268B1|2011-11-23|2020-09-29|Dow Global Technologies Llc|POLYMER BASED ON ETHYLENE, COMPOSITION AND ARTICLE|
    JP6042906B2|2011-12-22|2016-12-14|ダウ グローバル テクノロジーズ エルエルシー|Ethylene-based polymer having improved melt strength and process thereof|
    WO2014003783A1|2012-06-29|2014-01-03|Exxonmobil Chemical Patents Inc.|Dual modifiers in high pressure polyethylene processes to prevent reactor fouling|
    IN2015DN02921A|2012-09-28|2015-09-18|Dow Global Technologies Llc|
    KR102067312B1|2012-11-20|2020-01-16|다우 글로벌 테크놀로지스 엘엘씨|Low density ethylene-based polymers with high melt strength|
    JP6377141B2|2013-05-22|2018-08-22|ダウ グローバル テクノロジーズ エルエルシー|Low density ethylene-based compositions with improved melt strength, yield, and mechanical properties|
    ES2637970T3|2013-05-22|2017-10-18|Dow Global Technologies Llc|Low density ethylene based polymer compositions with high melt strength and medium-high density control|
    ES2717973T3|2013-12-26|2019-06-26|Dow Global Technologies Llc|Procedures for forming polymers based on ethylene using asymmetric polyenes|
    US9206293B2|2014-01-31|2015-12-08|Fina Technology, Inc.|Polyethyene and articles produced therefrom|
    CN105585765A|2014-10-20|2016-05-18|中国石油化工股份有限公司|Low density polyethylene resin for making high-transparency films and preparation method thereof|
    CN105585766A|2014-10-20|2016-05-18|中国石油化工股份有限公司|Low density polyethylene resin for medicinal film and preparation method thereof|
    KR101692123B1|2014-12-24|2017-01-02|한화토탈 주식회사|Method for manufacturing polyethylene resin for protective film|
    SG11201705241QA|2014-12-30|2017-07-28|Dow Global Technologies Llc|Process to control output and quality of ethylene-based polymer formed by high pressure free radical polymerization|
    US10400046B2|2015-06-25|2019-09-03|Joseph J. Matsko|Portable powered paint system|
    BR112017027866A2|2015-06-25|2018-08-28|Dow Global Technologies Llc|ethylene-based polymers with low hexane extractables|
    ES2786677T3|2015-06-25|2020-10-13|Dow Global Technologies Llc|Process for forming ethylene-based polymers|
    BR112017027794A2|2015-06-25|2018-08-28|Dow Global Technologies Llc|ethylene-based polymers with low hexane extractables and low densities|
    ES2774813T3|2015-06-25|2020-07-22|Dow Global Technologies Llc|Improved process to prepare high G'-wide and high MWD ethylene-based tubular polymers|
    CN107873035B|2015-06-30|2021-04-09|陶氏环球技术有限责任公司|High pressure free radical polymerization|
    EP3168237A1|2015-11-10|2017-05-17|Dow Global Technologies LLC|High pressure, free radical polymerizations to produce ethylene-based polymers|
    EP3168239A1|2015-11-10|2017-05-17|Dow Global Technologies LLC|High pressure free radical polymerizations|
    EP3238938A1|2016-04-29|2017-11-01|Borealis AG|Machine direction oriented films comprising multimodal copolymer of ethylene and at least two alpha-olefin comonomers|
    EP3260473A1|2016-06-24|2017-12-27|Dow Global Technologies LLC|High pressure, free radical polymerizations to produce ethylene-based polymers|
    WO2019022974A1|2017-07-28|2019-01-31|Dow Global Technologies Llc|Low density ethylene-based polymers for low speed extrusion coating operations|
    KR20190044005A|2017-10-19|2019-04-29|주식회사 엘지화학|Preparation method of polyethylene resin|
    WO2019078561A1|2017-10-19|2019-04-25|주식회사 엘지화학|Method for producing polyethylene resin|
    EP3938167A1|2019-03-14|2022-01-19|Braskem S.A.|Extrusion coating resin from tubular reactor|
    CN112250780B|2020-10-19|2021-09-07|浙江大学|Method for high pressure olefin polymerization|
    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-08-13| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2019-12-10| B07A| Technical examination (opinion): publication of technical examination (opinion)|
    2020-06-02| B09A| Decision: intention to grant|
    2020-10-20| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 21/09/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US38815210P| true| 2010-09-30|2010-09-30|
    US61/388,152|2010-09-30|
    PCT/US2011/052525|WO2012044504A1|2010-09-30|2011-09-21|Polymerization process to make low density polyethylene|
    [返回顶部]