WO2017172102A1 - Compositions polymères faiblement cristallines préparées dans un réacteur double - Google Patents

Compositions polymères faiblement cristallines préparées dans un réacteur double Download PDF

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WO2017172102A1
WO2017172102A1 PCT/US2017/018285 US2017018285W WO2017172102A1 WO 2017172102 A1 WO2017172102 A1 WO 2017172102A1 US 2017018285 W US2017018285 W US 2017018285W WO 2017172102 A1 WO2017172102 A1 WO 2017172102A1
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polymer
ethylene
propylene
reactor
film
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PCT/US2017/018285
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English (en)
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Danny Van Hoyweghen
Cynthia A. Mitchell
Achiel J.M. VAN LOON
Narayanaswami Dharmarajan
Sudhin Datta
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Exxonmobil Chemical Patents Inc.
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Priority to SG11201807680TA priority Critical patent/SG11201807680TA/en
Priority to CN201780018407.9A priority patent/CN108779305B/zh
Priority to EP17709516.3A priority patent/EP3436521B1/fr
Priority to CA3018952A priority patent/CA3018952C/fr
Priority to ES17709516T priority patent/ES2908980T3/es
Priority to JP2018551368A priority patent/JP6990661B2/ja
Publication of WO2017172102A1 publication Critical patent/WO2017172102A1/fr

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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/02—Heterophasic composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
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Definitions

  • This application relates to polymer compositions and processes for making thereof, prepared in a dual reactor.
  • the present invention relates to low crystalline polymer compositions and processes for making compositions.
  • Polymer compositions having a desirable balance of properties and attributes, leading to enhanced compositions that are useful in a number of applications, are generally sought.
  • Such composition enhancements can manifest themselves in a variety of ways depending on the specific application and the specific blend contemplated.
  • Such enhancements include, but are not limited to: (1) processibility in the molten state in such processes as milling, extrusion, calendering and injection molding; (2) initial physical properties in a solid state such as toughness, tack, adhesion, tear resistance, toughness, sealing, tensile and elongation; (3) improvements in the above-mentioned properties; and (4) long-term maintenance of such physical properties.
  • a variety of approaches have been suggested to obtain polymer compositions with the desired properties and attributes, but those approaches have experienced various shortcomings.
  • U.S. Patent No. 5,747,592 discloses a thermoplastic composition with polypropylene, rubber, and a plastomer.
  • U.S. Patent No. 8,618,033 discloses an ethylene copolymer with 40-70 wt% of units derived from ethylene and at least 30 wt% of units derived from at least one a-olefin having 3 to 20 carbons.
  • U.S. Patent No. 7,585,917 discloses a process for making thermoplastic blend compositions having a physical blend of a first polymer component, having polypropylene, and a second polymer component, having a reactor blend of a propylene polymer and an ethylene a-olefin elastomer.
  • U.S. Patent No. 6,207,756 discloses a polymer dispersion having a substantially amorphous elastomer and a semicrystalline plastic, prepared via a dual reactor in series (i.e., the individual components of the elastomer and semicrystalline are made in separate reactors).
  • U.S. Patent No. 6,319,998 also discloses a polymer blend made by a series reactor process. However, a series reactor process does not allow for much variability in the components produced in each of the reactors. In addition, series reactor process requires the use of a single catalyst.
  • a blend composition with a propylene polymer and an ethylene a-olefin elastomer, where the composition has a low melt index is suitable for use in film applications as a compatibilizer, where properties such as tear resistance and film toughness are sought.
  • a polymer blend composition comprising from about 65 wt% to about 90 wt% based on the total weight of the blend of an ethylene a-olefin elastomer having either no crystallinity or crystallinity derived from ethylene, having about 70 wt% or more units derived from ethylene; and from about 10 wt% to about 35 wt% based on the total weight of the blend of a propylene polymer having about 40 wt% or more units derived from propylene, including isotactically arranged propylene derived sequences; wherein the ethylene ⁇ -olefin elastomer and the propylene polymer are prepared in separate reactors arranged in parallel configuration.
  • Continuous When used to describe a process or an aspect of a process, e.g., a process step, the term “continuous” and its derivatives, including “continuously,” shall cover any process or step in which reagents and reacted products are supplied and removed continuously so that steady state, stable reaction conditions can be achieved.
  • polymer is the product produced by particular continuous polymerization in a particular polymerization zone or reactor.
  • Polymerization As used herein, the term "polymerization" to be given the broadest meaning used by persons skilled in the art refers to the conversion of monomer into polymer. Polymerization zone refers to the zone in which polymerization takes place and is generally formed by a back mixed reactor for forming a substantially random polymer.
  • Polysplit shall mean the calculated result of the weight of the first polymer (ethylene polymer) that is produced from the first polymerization zone divided by the combined weight of the first polymer and the second polymer (propylene polymer).
  • ethylene polymer ethylene polymer
  • the ethylene polymer is always regarded as the numerator.
  • Tm melting point
  • heats of fusion which properties can be influenced by the presence of comonomers or steric impurities that hinder the formation of crystallites by the polymer chains. Measurements were performed on a Pyris 1 Differential Scanning Calorimeter. Samples may be tested in the form of powders, granules, pellet, film, sheet and molded specimens. Sample weight for measurement is 5 +/- 0.5 mg. Materials were tested from -20°C to 18°0C at 10°C/min rates. Melting temperature and heat of fusion are taken from the 2nd Melt. The thermal output is recorded as the area under the melting peak of the sample and is measured in Joules as a measure of the heat of fusion. The melting point is recorded as the temperature of the greatest heat absorption within the range of melting of the sample.
  • Comonomer Content The comonomer content of the polymer is measured using
  • 13C nuclear magnetic resonance The 13C solution NMR was performed on a 10mm broadband probe at a field of at least 600MHz in tetrachloroethane-d2 solvent at 120°C with a flip angle of 90° and full NOE with decoupling.
  • Sample preparation (polymer dissolution) was performed at 140°C where 0.20 grams of polymer was dissolved in an appropriate amount of solvent to give a final polymer solution volume of 3mL. Chemical shifts were referenced by setting the most intense propylene methyl group signal to 21.83 ppm.
  • composition calculations of the ethylene propylene copolymer are described by Randall in "A Review Of High Resolution Liquid 13Carbon Nuclear Magnetic Resonance Characterization of Ethylene-Based Polymers", Polymer Reviews, 29:2, pp. 201-317 (1989).
  • Mw, Mn and Mw/Mn are determined by using a High Temperature Gel Permeation Chromatography (Agilent PL-220), equipped with three in-line detectors, a differential refractive index detector (DRI), a light scattering (LS) detector, and a viscometer. Experimental details, including detector calibration, are described in: T. Sun, P. Brant, R. R. Chance, and W. W. Graessley, Macromolecules, Volume 34, Number 19, pp. 6812-6820, (2001) and references therein. Three Agilent PLgel ⁇ Mixed-B LS columns are used. The nominal flow rate is 0.5 mL/min, and the nominal injection volume is 300 ⁇ .
  • the various transfer lines, columns, viscometer and differential refractometer (the DRI detector) are contained in an oven maintained at 145°C.
  • Solvent for the experiment is prepared by dissolving 6 grams of butylated hydroxy toluene as an antioxidant in 4 liters of Aldrich reagent grade 1,2,4-trichlorobenzene (TCB). The TCB mixture is then filtered through a 0.1 ⁇ Teflon filter. The TCB is then degassed with an online degasser before entering the GPC-3D.
  • Polymer solutions are prepared by placing dry polymer in a glass container, adding the desired amount of TCB, then heating the mixture at 160°C with continuous shaking for about 2 hours. All quantities are measured gravimetrically.
  • the TCB densities used to express the polymer concentration in mass/volume units are 1.463 g/ml at room temperature and 1.284 g/ml at 145°C.
  • the injection concentration is from 0.5 to 2.0 mg/ml, with lower concentrations being used for higher molecular weight samples.
  • Prior to running each sample the DRI detector and the viscometer are purged. Flow rate in the apparatus is then increased to 0.5 ml/minute, and the DRI is allowed to stabilize for 8 hours before injecting the first sample.
  • the LS laser is turned on at least 1 to 1.5 hours before running the samples.
  • the concentration, c, at each point in the chromatogram is calculated from the baseline-subtracted DRI signal, 3 ⁇ 4RI, using the following equation:
  • c K DRI I DRI /(dn/dc)
  • K DRI is a constant determined by calibrating the DRI
  • (dn/dc) is the refractive index increment for the system.
  • the LS detector is a Wyatt Technology High Temperature DAWN HELEOS.
  • the molecular weight, M, at each point in the chromatogram is determined by analyzing the LS output using the Zimm model for static light scattering (M.B. Huglin, LIGHT SCATTERING FROM POLYMER SOLUTIONS, Academi
  • AR(9) is the measured excess Rayleigh scattering intensity at scattering angle ⁇
  • c is the polymer concentration determined from the DRI analysis
  • a 2 is the second virial coefficient
  • ⁇ ( ⁇ ) is the form factor for a monodisperse random coil
  • K Q is the optical constant for the system:
  • N A is Avogadro's number
  • (dn/dc) is the refractive index increment for the system, which take the same value as the one obtained from DRI method.
  • a high temperature Viscotek Corporation viscometer which has four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers, is used to determine specific viscosity.
  • One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides of the bridge, measures a differential pressure.
  • the specific viscosity, ⁇ 8 for the solution flowing through the viscometer is calculated from their outputs.
  • the intrinsic viscosity, [ ⁇ ] at each point in the chromatogram is calculated from the following equation:
  • the branching index (g' v i s ) is calculated using the output of the GPC-DRI-LS-VIS method as follows.
  • the average intrinsic viscosity, [ ⁇ ] ⁇ 8 , of the sample is calculated by: ⁇ c i hi
  • the branching index g' vjs is defined as:
  • M v is the viscosity-average molecular weight based on molecular weights determined by LS analysis.
  • Mooney Viscosity a term used to characterize certain polymers, polymer components, and polymer compositions herein.
  • Mooney Viscosity ML (1+4) at 125°C
  • Mooney Viscosity simply "Mooney Viscosity,” to be defined and measured according to the definition and measurement procedure set forth in U.S. Patent No. 6,686,415, which is hereby incorporated by reference in its entirety.
  • any "Mooney Viscosity" value referenced herein is deemed to encompass any Mooney Viscosity measured in accordance with any recognized, published procedure for measuring Mooney Viscosity.
  • MI Magnetic Reduction Tube
  • MI Melt Index
  • the units for "MI” are grams per 10 minutes and the test to be herein for determining MFR/MI is set forth in any version and condition set forth in ASTM-1238 that uses 2.16 kg at 190°C.
  • the ethylene polymer is present in the composition in an amount of more than 65 wt% based on the total weight of the polymer composition.
  • compositions described herein further comprises a filler, or a plasticizer, or both.
  • the polymer composition is substantially free from diene units.
  • the ethylene polymer is a low crystalline ethylene propylene copolymer.
  • the blend is a reactor blend formed in a parallel process.
  • One of the components or elements in certain compositions is a blend.
  • the composition is a reactor blend.
  • the reactor blends include at least a first polymer (ethylene polymer) and a second polymer (propylene polymer), as discussed below.
  • first polymer ethylene polymer
  • second polymer propylene polymer
  • a reactor blend herein distinguished from a “physical blend”, the latter being the combination of two or more polymers that have already been formed and recovered before being mixed or otherwise combined, e.g., separated (which would preferably also include being devolatilized) from some or all of the remaining polymerization mixture (e.g., unreacted monomers and/or solvent) and then combined together.
  • reactor blend does not preclude (except to the extent stated otherwise) two components that have reacted to some extent or degree with one another, e.g., where one is a reaction product that is derived from the other, in whole or in part.
  • reactor blend preclude two components that are mixed together but that can be separated by conventional means (e.g., fractionation) following formation and therefore can be identified as distinct polymers, e.g., a semicrystalline polymer having a distinct melting point (Tra) and an atactic or amorphous ethylene elastomer having either a low melting point (Tra) or no melting point.
  • reactor blend used herein may in certain embodiments refer to a homogenous (e.g., a single phase) material while in other embodiments it may refer to a multiphase blend (e.g., two or more distinct phases).
  • a blend formed by melt-blending or dry-blending is a physical blend.
  • the reactor blend compositions preferably include at least a propylene polymer and an ethylene polymer, although the ethylene polymer is in some cases identifiable by inference and/or by fractionation.
  • the reactor blend includes a major portion by weight (more than 65 wt%) ethylene polymer with a minor portion (less than 35 wt%) propylene polymer.
  • the first polymer and second polymer form a substantially homogenous reactor blend, meaning that the first polymer and second polymer are part of, or are within, or occupy, the same phase.
  • the first polymer and second polymer form distinct phases of a multiphase composition.
  • a reactor blend includes a continuous phase (either the first polymer or the second polymer), which may be a dispersed phase (dispersion) and a discontinuous phase (either the first polymer or the second polymer), which may be a matrix phase.
  • a continuous phase or the dispersed phase may represent a major portion of the reactor blend.
  • At least one embodiment of the reactor blend is a multiphase composition having a continuous phase that includes first polymer as a minor portion of the reactor blend and a dispersed phase that includes second polymer as a major portion.
  • the second polymer can be crosslinked. The various polysplit ranges identified above may be used.
  • the blends described herein are formed in either batch or continuous "multistage polymerization,” meaning that two (or more) different polymerizations (or polymerization stages) are conducted. More specifically, a multistage polymerization may involve either two or more sequential polymerizations (also referred to herein as a “series process” two or more parallel polymerizations (also referred to herein as a "parallel process”). Preferably, the polymerization is conducted in a parallel process.
  • the polymers made in the respective reactors of the continuous, multiple reactor solution plant are blended when in solution without prior isolation from the solvent.
  • the blends may be the result of series reactor operation, where the effluent of a first reactor enters a second reactor and where the effluent of the second reactor can be submitted to finishing steps involving devolatilization.
  • the blend may also be the result of parallel reactor operation where the effluents of both reactors are combined and submitted to finishing steps. Either option provides an intimate admixture of the polymers in the devolatilized blend. Either case permits a wide variety of polysplits to be prepared whereby the proportion of the amounts of polymers produced in the respective reactors can be varied widely.
  • the blends described herein include a first polymer component (first polymer), which preferably is (or includes) an elastomer that is predominantly ethylene, i.e., having more than 30 wt% or 40 wt%, or 50 wt% units derived from ethylene monomer.
  • first polymer preferably is (or includes) an elastomer that is predominantly ethylene, i.e., having more than 30 wt% or 40 wt%, or 50 wt% units derived from ethylene monomer.
  • the crystallinity, and hence other properties as well, of the first polymer are preferably different from those of the second polymer.
  • the polymers described herein are predominantly ethylene, i.e., having more than 70 wt% units derived from ethylene monomer.
  • the ethylene content of the ethylene polymer is greater than or equal to about 65 wt%, preferably greater than about 70 wt%, or 75 wt% to less than about 85 wt% or about 90 wt%.
  • the ethylene polymer has a propylene content of less than about 30 wt%, preferably 25%, or 23 wt% to greater than about 15 wt% or about 10 wt%.
  • the ethylene polymer has a C4-C20 a-olefin content of less than about 5 wt%.
  • the first polymer (also referred to as the "ethylene polymer”) has some crystalline (including “semi-crystalline”), also referred to herein as "crystallinity derived from ethylene.”
  • any crystallinity of the first polymer is preferably derived from the ethylene. The percent crystallinity in such cases is measured as a percentage of polyethylene crystallinity and thus the origin of the crystallinity from ethylene is established.
  • the first polymer in addition to units derived from ethylene, also includes units derived from an a-olefin monomer.
  • Suitable a-olefin monomers include, but are not limited to propylene, butene, pentene, hexene, heptene, or octene, and their isomers.
  • the first polymer can be formulated using different a-olefin monomers, selected from the list above, and/or different amounts of monomers, e.g., ethylene and a- olefin monomers, to prepare different types of polymers, e.g., ethylene polymers having desired properties.
  • the first polymer is formed during (or by) the first polymerization, which in the case of a parallel process, involving parallel polymerization and/or parallel reactors, the "first polymer” may be formed at the same time as the "second polymer," but the product streams (still including solvent) are combined after the first and second polymers are sufficiently formed.
  • One purpose of the first polymer is to enhance the attributes of the second polymer.
  • Such enhancements can manifest themselves in a variety of ways depending on the specific application and the specific blend contemplated.
  • Such enhancements include, but are not limited to, improvements in cure rate and state; processability as defined by such processes as milling, extrusion, calendering and injection molding; physical properties such as toughness, tack, adhesion, tear resistance, tensile and elongation and heat aging as defined by the retention of such physical properties at elevated temperatures.
  • the blends herein preferably include at least a propylene polymer, which is preferably the polymer formed by a second polymerization reaction (under conditions described elsewhere herein) and preferably in a "second reactor" part of a parallel process.
  • the propylene polymer should have (at minimum) 40 wt% propylene units, and preferably more, as noted below.
  • the propylene polymer is preferably a polypropylene copolymer having 60 wt% or more units derived from propylene, having isotactically arranged propylene derived sequences and having a heat of fusion less than 45 J/g.
  • the polypropylene copolymer preferably has at least 5 wt% non-propylene comonomer units, e.g., ethylene units, and more preferably at least 10 wt% or more ethylene units.
  • the propylene polymer preferably comprises >60 wt%, more preferably >75 wt% propylene-derived units. In some embodiments, the propylene polymer comprises from 75-95 wt% of propylene-derived units, more preferably from 80-90 wt% of propylene-derived units, the balance comprising one or more a-olefins.
  • a-olefin ranges include 5-25 wt%, more preferably 7-25 wt%, more preferably 7.5-25 wt%, more preferably 7.5-17.5 w% and more preferably 8-17.5 wt% (based on the weight of propylene and a-olefin).
  • a preferred a-olefin is ethylene.
  • the propylene polymer preferably has a MFR ⁇ about 800, more preferably ⁇ about 500, more preferably ⁇ about 200, more preferably ⁇ about 100, more preferably ⁇ about 50.
  • Particularly preferred embodiments include a propylene polymer with an MFR of from about 1 -25, more preferably about 1-20.
  • the crystallinity of the first polymer should be derived from isotactic polypropylene sequences. The isotacticity of the propylene polymer can be illustrated by the presence of a preponderance of the propylene residues in the polymer in mm triads.
  • the tacticity of the propylene polymer is preferably greater than the tacticity of either the reactor blend or the ethylene polymer, e.g., where the propylene polymer is isotactic and the ethylene polymer is atactic.
  • the crystallinity of the propylene polymer can be expressed in terms of heat of fusion.
  • the propylene polymer of the invention can have a heat of fusion, as determined by
  • the heat of fusion of the propylene polymer is less than 45 J/g.
  • the propylene polymer has generally isotactic crystallizable propylene sequences, and the above heats of fusion are believed to be due to the melting of these crystalline segments.
  • the level of crystallinity of the propylene polymer can also be reflected in its melting point.
  • the propylene polymer has a single melting point.
  • a sample of propylene copolymer will often show secondary melting peaks adjacent to the principal peak. The highest peak is considered the melting point.
  • the propylene polymer described herein can have a melting point by DSC within the range having an upper limit of 115°C, or 110°C, or 105°C, or 90°C, or 80°C, or 70°C, and a lower limit of 0°C, or 20°C, or 25°C, or 30°C, or 35°C, or 40°C, or 45°C.
  • the propylene polymer has a melting point of less than 105°C, and more preferably less than 100°C, and even more preferably less than 90°C. Also, it is preferred that the propylene polymer have a melting point greater than about 25°C, or 40°C.
  • At least 75% by weight of the polymer, or at least 80% by weight, or at least 85% by weight, or at least 90% by weight, or at least 95% by weight, or at least 97% by weight, or at least 99% by weight of the polymer is soluble in a single temperature fraction, or in two adjacent temperature fractions, with the balance of the polymer in immediately preceding or succeeding temperature fractions.
  • These percentages are fractions, for instance in hexane, beginning at 23°C and the subsequent fractions are in approximately 8°C increments above 23°C. Meeting such a fractionation requirement means that a polymer has statistically insignificant intermolecular differences of tacticity of the polymerized propylene.
  • the percentage of mm triads in the propylene polymer is in the range having an upper limit of 98%, or 95%, or 90%, or 85%, or 82%, or 80%, or 75%, and a lower limit of 50%, or 60%.
  • Certain propylene polymers have an isotacticity index greater than 0%, or within the range having an upper limit of 50%, or 25% and a lower limit of 3%, or 10%.
  • Certain propylene polymers can have a tacticity index (m/r) within the range having an upper limit of 800, or 1000, or 1200, and those polymers may have a lower limit of 40, or 60.
  • the second polymerization may in certain cases be conducted in the presence of an a-olefin; thus the resulting polymer formed when such a-olefin is present will include
  • a-olefins C3-C20 a-olefins, including, but not limited to, propylene; butene-1 ; pentene-1,2- methylpentene- 1 ,3-methylbutene- 1 ; hexene- 1 ,3-methylpentene- 1 ,4-methylpentene- 1,3,3- dimethylbutene-1; heptene-1 ; hexene- 1 ; dimethylpentene-1 trimethylbutene-1; ethylpentene-1; octene-1 ; methylpentene-1 ; dimethylhexene-1; trimethylpentene-1 ; ethylhexene-1; methylethylpen
  • the composition is a reactor blend.
  • the method discussed below has the advantage of eliminating the need for a melt blending operation and enables intimate blends of the copolymers to be made in the original reaction medium. Such materials have unique properties because they are not subjected to shear degradation in melt processing equipment. The degree of dispersion of each component of the blend is more intimate.
  • the plant productivity is controlled by the bottleneck presented by the recycle system.
  • the residence time of each reactor can be chosen independently as long as the total solvent flow does not exceed the recycle capacity.
  • That effluent stream can be composed of polymer produced from the polymerization as well as catalyst and any unreacted monomers.
  • Each effluent stream can be characterized as having a particular polymer concentration.
  • the polymer concentration in the effluent of each reactor can be maintained in the range of 1 to 30% by weight or between 3 to 20% by weight, based on the total weight of the particular effluent.
  • the polymer concentration of the effluent from each of the two reactors preferably represents the polymer made in that reactor alone (which can be measured, for example, by separating the formed polymer from non-polymer materials).
  • Polymer concentration of the combined effluent represents all the polymer material present in the two reactors, measured at a given time, e.g., after a particular residence time or some other set point.
  • That polymer material includes at least the reactor blend, which may include a certain amount of the propylene polymer together with at least one other polymer, e.g., an ethylene polymer or a reaction product of the other reactants themselves, e.g., the monomers, or both forms of reactant product.
  • the first effluent polymer concentration range from a low of 1 wt%, or 2 wt%, or 3 wt%, or 4 wt%, or 5 wt%, or 6 wt%, to a high of 30 wt%, or 25 wt%, or 20 wt%, or 16 wt%, or 12 wt%, or 8 wt%.
  • the combined effluent polymer concentration range from a low of 3 wt%, or 4 wt%, or 5 wt%, or 6 wt%, or 7 wt%, or 8 wt%, to a high of 30 wt%, or 25 wt%, or 20 wt%, or 18 wt%, or 16 wt%, or 14 wt%.
  • a polymer can be recovered from the effluent of either reactor or the combined effluent, by separating the polymer from other constituents of the effluent.
  • polymer can be recovered from effluent by coagulation with a nonsolvent such as isopropyl alcohol, acetone, or n-butyl alcohol, or the polymer can be recovered by stripping the solvent or other media with heat or steam.
  • a nonsolvent such as isopropyl alcohol, acetone, or n-butyl alcohol
  • One or more conventional additives such as antioxidants can be incorporated in the polymer during the recovery procedure.
  • Possible antioxidants include phenyl-beta- naphthylamine; di-tert-butylhydroquinone, triphenyl phosphate, heptylated diphenylamine, 2,2'-methylene-bis(4-methyl-6-tert-butyl)phenol, and 2,2,4-trimethyl-6-phenyl-l ,2- dihydroquinoline.
  • Other methods of recovery such as by the use of lower critical solution temperature (LCST) followed by devolatilization are also envisioned.
  • LCST critical solution temperature
  • the molecular weight characteristics (e.g., Mw, Mn, etc.) of the reactor blend and also of the individual-propylene polymer and ethylene polymer (polymer components) can in certain circumstances be adjusted depending upon the desired properties of the reactor blend. Those molecular weight characteristics are described elsewhere herein.
  • the molecular weight characteristics of each polymer can be set by choosing the reactor temperature, monomer concentration, and by optionally adding chain transfer agents such as hydrogen. Also, molecular weight can generally be lowered by increasing reaction temperatures, and raised by increasing monomer concentrations.
  • the compositions can be prepared using any SSC (single sited catalyst).
  • a catalyst may be a transition metal complex generally containing a transition metal Groups 3 to 10 of the Periodic Table; and at least one ancillary ligand that remains bonded to the transition metal during polymerization.
  • the transition metal is used in a reduced cationic state and stabilized by a cocatalyst or activator.
  • the ancillary ligand may be a structure capable of forming a . ⁇ bond such a cyclopentadienyl type ring structure.
  • the ancillary ligand may also be a pyridinyl or amide ligand.
  • the transition metal is preferably of Group 4 of the Periodic table such as titanium, hafnium or zirconium which are used in polymerization in the d° mono-valent cationic state and have one or two ancillary ligands as described in more detail hereafter.
  • the important features of such catalysts for coordination polymerization are the ligand capable of abstraction and that ligand into which the ethylene (olefinic) group can be inserted.
  • the transition metal complex may impose a degree of steric order on the propylene monomer by suitable chirality.
  • first polymers of higher molecular weight are desired or higher polymerization temperatures, it is preferable to a non- or weakly coordinated anion (the term non-coordinating anion as used herein includes weakly coordinated anions) as cocatalyst.
  • aluminoxanes or complexes incorporating oxy-aluminum moieties may be used.
  • a precursor for the non-coordinating anion may be used with a transition metal complex supplied in a reduced valency state.
  • the precursor may undergo a redox reaction.
  • the precursor may be neutral, such as a borane complex and form the transition metal cation by abstracting a ligand from it.
  • the precursor may be an ion pair of which the precursor cation, such as a borate, is neutralized and/or eliminated in some manner.
  • the precursor cation may be an ammonium salt as in EP 277 003 and EP 277 004.
  • the precursor cation may be a triphenyl carbonium derivative as in EP 426 637.
  • the non-coordinating anion can be a Group 10-14 complex wherein boron or aluminum is the charge bearing atom shielded by ligands which may be halogenated and especially perfuorinated.
  • ligands which may be halogenated and especially perfuorinated.
  • tetra-aryl- substituted Group 10-14 non-carbon element-based anion especially those that are have fluorine groups substituted for hydrogen atoms on the aryl groups, or on alkyl substituents on those aryl groups.
  • the non-coordinating anion may be used in approximately equimolar amounts relative to the transition metal complex, such as at least 0.25, preferably 0.5, and especially 0.8 and such as no more than 4, preferably 2 and especially 1.5.
  • the transition metal complex may be a pyridine amine complex useful for olefin polymerization such as those described in WO 03/040201.
  • the transition metal complex may a fluxional complex which undergoes periodic intra-molecular re-arrangement so as to provide the desired interruption of stereoregularity as in U. S. Patent No. 6,559,262.
  • the transition metal complex may be a stereorigid complex with mixed influence on propylene insertion, see EP 1070087.
  • the transition metal complex is a chiral bridged bis cyclopentadienyl derivative having the formula L A L B L C iMDE where L A and L B are substituted or unsubstituted cyclopentadienyl or hetero-cyclopentadienyl ancillary ligand ⁇ -bonded to M in which the L A
  • L ligands are covalently bridged together through a Group 14 element linking group; L i is an optional neutral, non-oxidizing ligand having a dative bond to M (i equals 0 to 3); M is a Group 4 or 5 transition metal; and, D and E are independently mono-anionic labile ligands, each having a ⁇ -bond to M, optionally bridged to each other or L A or L B .
  • the mono-anionic ligands are displaceable by a suitable activator to permit insertion of a polymerizable monomer or macro-monomer can insert for coordination polymerization on the vacant coordination site of the transition metal component.
  • the total catalyst system will generally additionally comprise one or more organo-metallic compound as scavenger.
  • organo-metallic compound as scavenger.
  • Such compounds as used in this application is meant to include those compounds effective for removing polar impurities from the reaction environment and for increasing catalyst activity.
  • a polymerization process consists of or includes a polymerization in the presence of a catalyst including a bis(cyclopentadienyl) metal compound and either (1) a non-coordinating compatible anion activator, or (2) an alumoxane activator.
  • a catalyst including a bis(cyclopentadienyl) metal compound and either (1) a non-coordinating compatible anion activator, or (2) an alumoxane activator.
  • catalyst systems which can be used are described in U. S. Patent Nos. 5, 198,401 and 5,391,629.
  • an alumoxane activator can be used in an amount to provide a molar aluminum to metallocene ratio of from 1 : 1 to 20,000: 1.
  • a non- coordinating compatible anion activator can be used in an amount to provide a molar ratio of biscyclopentadienyl metal compound to non-coordinating anion of from 10: 1 to 1 : 1.
  • the polymerization reaction is conducted by reacting monomers in the presence of a catalyst system described herein at a temperature of from 0°C to 200°C for a time of from 1 second to 10 hours.
  • the propylene polymer of the present invention may be produced in the presence of a chiral metallocene catalyst with an activator and optional scavenger.
  • a chiral metallocene catalyst with an activator and optional scavenger.
  • single site catalysts is preferred to enhance the homogeneity of the polymer. As only a limited tacticity is needed many different forms of single site catalyst may be used. Possible single site catalysts are metallocenes, such as those described in U. S. Pat. No.
  • 5,026,798 which have a single cyclopentadienyl ring, advantageously substituted and/or forming part of a polycyclic structure, and a hetero-atom, generally a nitrogen atom, but possibly also a phosphorus atom or phenoxy group connected to a group 4 transition metal, preferably titanium but possibly zirconium or hafnium.
  • a further example is MesCpTiMes activated with B(CF) 3 as used to produce elastomeric polypropylene with an Mn of up to 4 million. See Sassmannshausen, Bochmann, Rosch, Lilge, J. Organomet. Chem. (1997) 548, 23-28.
  • metallocenes which are bis cyclopentadienyl derivatives having a group transition metal, preferably hafnium or zirconium. Such metallocenes may be unbridged as in U.S. Patent No. 4,522,982 or U.S. Patent No. 5,747,621. The metallocene may be adapted for producing a polymer comprising predominantly propylene derived units as in U.S. Patent No. 5,969,070 which uses an unbridged bis(2 -phenyl indenyl) zirconium dichloride to produce a homogeneous polymer having a melting point of above 7°9C.
  • the cyclopentadienyl rings may be substituted and/or part of poly cyclic systems as described in the above U.S. patents.
  • metallocenes include those in which the two cyclopentadienyl groups are connected through a bridge, generally a single atom bridge such as a silicon or carbon atom with a choice of groups to occupy the two remaining valencies. Such metallocenes are described in U.S. Patent No.
  • the manner of activation of the single site catalyst can vary.
  • Alumoxane and preferably methyl alumoxane can be used.
  • Higher molecular weights can be obtained using non-or weakly coordinating anion activators (NCA) derived and generated in any of the ways amply described in published patent art such as EP 277 004, EP 426 637, and many others.
  • NCA non-or weakly coordinating anion activators
  • Activation generally is believed to involve abstraction of an anionic group such as the methyl group to form a metallocene cation, although according to some literature zwitterions may be produced.
  • the NCA precursor can be an ion pair of a borate or aluminate in which the precursor cation is eliminated upon activation in some manner, e.g., trityl or ammonium derivatives of tetrakis pentafluorophenyl boron (See EP 277 004).
  • the NCA precursor can be a neutral compound such as a borane, which is formed into a cation by the abstraction of and incorporation of the anionic group abstracted from the metallocene (See EP 426 638).
  • polymerizations in the different reactors may in certain embodiments be conducted in the presence of the same catalyst mixtures, and in other embodiments be conducted in the presence of different catalyst mixtures.
  • catalyst mixture includes at least one catalyst and at least one activator, although depending on the context, any reference herein to "catalyst” usually also implies an activator as well.
  • the appropriate catalyst mixture may be delivered to the respective reactor in a variety of ways. For example, it may be delivered as a solution or slurry, either separately to the reactor, activated in-line just prior to the reactor, or preactivated and pumped as an activated solution or slurry to the reactor. Polymerizations are carried out in each reactor, in which reactant components (e.g., desired monomers, comonomers, catalyst/activators, scavengers, and optional modifiers) are preferably added continuously to the appropriate reactor.
  • reactant components e.g., desired monomers, comonomers, catalyst/activators, scavengers, and optional modifiers
  • both catalyst mixtures are added to the first reactor, while in other embodiments one catalyst mixture is added to the first reactor and a different catalyst mixture is added to the second reactor (although in a sequential operation at least some of the first catalyst mixture from the first reactor may be directed to the second reactor together with the product mixture from the first reactor.
  • two different catalysts are added as part of different reactant feeds, e.g., a "first catalyst,” which may be part of a "first reactant feed,” and a “second catalyst,” which may be part of a “second reactant feed,” although in at least certain embodiments (e.g., series reactors) both first and second catalysts are present to some degree in the second reactor feed, e.g., when the first effluent is supplied to a second reactor.
  • the first catalyst is a chiral catalyst while the second catalyst is a non-chiral catalyst.
  • the same catalyst mixture can be used for each of the first and second polymerizations, whether series or parallel.
  • certain catalyst mixtures described in U.S. Patent No. 6,207,756 can be used in both polymerizations, and that patent is hereby incorporated by reference in its entirety, particularly the portions describing the catalyst mixtures, e.g., column 8 line 20 through column 14, line 21.
  • Preferred catalysts are those that are isospecific.
  • the first catalyst is preferably 1 , -bis(4-triethylsilylphenyl)methylene- (cyclopentadienyl)(3,8-di -tertiary -butyl- 1 -fluroenyl)hafnium dimethyl with dimethylaninliniumtetrakis(pentafluorophenyl)borate activator.
  • the second catalyst is preferably dimethylsilylbis(indenyl)hafiiium dimethyl with dimethylaniliniumtetrakis(heptafluoronaphthyl)borate activator.
  • compositions herein are particularly useful for film applications.
  • the film can be a mono layer or multi-layer film.
  • the film comprises at least one layer, whether the only layer of the mono-layer film or a layer of a multi-layer film, comprising of from about 5 wt% to about 95 wt% of the polymer composition based on the total weight of the film layer.
  • that film layer has a thickness of about 1 ⁇ to about 2,000 ⁇ ; about 5 ⁇ to about 150 ⁇ ; and about 10 ⁇ to about 100 ⁇ ; and about 20 ⁇ to about 90 ⁇ ; and about 15 ⁇ to about 75 ⁇ . If part of a multi-layer film structure, the film layer makes up at least 5% of the total film thickness, or at least 10%, or at least 15%, or at least 17%, or at least 20%, or at least 50% of the total film thickness.
  • the films can be formed by any number of well-known lamination, extrusion or coextrusion techniques. Any of the blown, tentered or cast film techniques commonly used is suitable.
  • a resin composition can be extruded in a molten state through a flat die and then cooled to form a film, in a cast film process.
  • the composition can be extruded in a molten state through an annular die and then blown and cooled to form a tubular, blown film, which can then be used to make sacks or slit and unfolded to form a flat film.
  • Films with the polymer composition of the invention are expected to possess an excellent balance of mechanical properties, toughness, sealability and cling/adhesive properties.
  • the films can also be used for shrink films and form fill and seal applications requiring abuse resistance.
  • the films also possess good softness/feel and optical/clarity properties useful for food packaging at any temperature.
  • Specific applications include trash bags, adult care items, agricultural films, aluminum foil laminates, aluminum laminates, asphalt films, auto panel films, bacon packaging, bag-in-box liquid packaging applications, bakery goods, banana film, batch inclusion bags, bathroom tissue overwrap, biaxially oriented films, biaxially oriented polypropylene (BOPP) films, biscuits packages, boutique bags, bread bags, bubble wrap, building film, cake mix packaging, can liners, candy wrap, cardboard liquid packaging, carpet film, carry-out sacks, cement packaging, cereal liners, cheese packaging, chemical packaging, clarity films, coffee packaging, coin bags, collation shrink films, confectionary packaging, construction sheeting, construction film, consumer goods, consumer trash bags, continuous wrap, convenience packaging, cosmetics packaging, counter bags, cover film, cup/cutlery overwrap, deli and bakery wrap, detergent packaging, diaper backsheet, disposables (diapers, sanitary, etc.), dry food packaging, dry grains, dunnage bags, fertilizer, fish & seafood packaging, food packaging, foundation film, freeze-dried products, freezer
  • the blends described herein will find utility in other applications like, but not limited to extrusion coating, injection molding, rotomolding, and blow molding applications.
  • Physical properties of the film can vary from those of the polymer composition, depending on the film forming techniques used. Certain unique properties of the films are described in more detail below.
  • P-l and P-2 are comparative metallocene-catalyzed ethylene- propylene polymers prepared in a single reactor.
  • P-l and P-2 were polymerized by the process described herein. Copolymerizations were carried out in a single-phase, liquid-filled, stirred tank reactor with continuous flow of feeds to the system and continuous withdrawal of products under equilibrium conditions. All polymerizations were done in a solvent comprising predominantly e alkanes, referred to generally as hexane solvent, using soluble metallocene catalysts and discrete, non- coordinating borate anion as co-catalysts.
  • a homogeneous dilute solution of tri-n-octyl aluminum in hexane was used as a scavenger in concentrations appropriate to maintain reaction. Hydrogen, was added, if necessary, to control molecular weight.
  • the hexane solvent was purified over beds of 3A mole sieves and basic alumina. All feeds were pumped into the reactors by metering pumps, except for the ethylene, which flowed as a gas through a mass flow meter/controller. Reactor temperature was controlled adiabatically by controlled chilling of the feeds and using the heat of polymerization to heat the reactor. The reactors were maintained at a pressure in excess of the vapor pressure of the reactant mixture to keep the reactants in the liquid phase.
  • P-4 and P-5 were inventive metallocene-catalyzed ethylene-propylene copolymers.
  • the first ethylene-rich polymer was prepared in a first reactor, the second propylene-rich polymer was prepared in a second reactor, and the ethylene-rich polymer and propylene-rich polymer were reactor blended.
  • the first reactor had 1, l '-bis(4- triethylsilylphenyl)methylene-(cyclopentadienyl)(3,8-di-tertiary-butyl-l -fluroenyl)hafnium dimethyl catalyst and dimethylaninliniumtetrakis(pentafluorophenyl)borate activator.
  • the second reactor had dimethylsilylbis(indenyl)hafhium dimethyl catalyst and dimethylaniliniumtetrakis(heptafluoronaphthyl)borate activator.
  • P-4 through P-5 were polymerized by the process described herein. Copolymerizations were carried out in two single-phase liquid-filled, stirred tank reactors with continuous flow of feeds to the system and continuous withdrawal of products under equilibrium conditions, configured in parallel. All polymerizations were done in a solvent comprising predominantly e alkanes, referred to generally as hexane solvent, using soluble metallocene catalysts and discrete, non-coordinating borate anion as co-catalysts. Hydrogen, was added, if necessary, to control molecular weight. The hexane solvent was purified over beds of 3A mole sieves and basic alumina.
  • Reactor temperature was controlled adiabatically by controlled chilling of the feeds and using the heat of polymerization to heat the reactor.
  • the reactors were maintained at a pressure in excess of the vapor pressure of the reactant mixture to keep the reactants in the liquid phase. In this manner the reactors were operated liquid full in a homogeneous single phase.
  • Ethylene and propylene feeds were mixed with a pre-chilled hexane solvent stream.
  • a hexane solution of a tri-n-octyl aluminum scavenger was added to the combined solvent and monomer stream just before it entered the reactor to further reduce the concentration of any catalyst poisons.
  • a mixture of the catalyst components in solvent was pumped separately to the reactor and entered through a separate port.
  • the reaction mixture was stirred aggressively to provide thorough mixing over a broad range of solution viscosities. Flow rates were set to maintain an average residence time in the reactor of about 10 minutes.
  • the copolymer mixture from each reactor was combined and subjected to quenching, a series of concentration steps, heat and vacuum stripping and pelletization, the general conditions of which are described in International Patent Publication WO 99/45041 , incorporated herein by reference in its entirety. Properties of P-4 through P-5 are included below in Table 1 and were measured according to the methods described herein.
  • P-3 is VistalonTM805, an ethylene polymer commercially available from ExxonMobil Chemical Company.
  • C-l and C-2 are physical blends of commercial ethylene polymer and propylene polymers, available from ExxonMobil Chemical Company.
  • C-l is a physical blend of 90 wt% VistalonTM805 and 10 wt% VistamaxxTM3020.
  • C-2 is a physical blend of 90 wt%
  • VistalonTM805 and 10 wt% VistamaxxTM6100 were physically blended in a ZSK twin screw extruder.
  • the batch size for twin screw compounding was 30 kg.
  • Compounding in the ZSK extruder was accomplished by tumble- blending the two components (listed in Table 1) in a V-cone blender and introducing the blend into the extruder hopper.
  • the melt temperature was maintained at 230°C.
  • a five layer film having a total thickness of 50 ⁇ was prepared. Each film had an outside bubble skin layer (thickness of 12.5 ⁇ ), subskin layer (thickness of 6.25 ⁇ ), core layer (thickness of 12.5 ⁇ ), subskin layer (thickness of 6.25 ⁇ ), and inside bubble skin layer (thickness of 12.5 ⁇ ) was formed.
  • the seven film samples are detailed below in Table 2.
  • each film sample was tested for the following film properties: force, elongation, seal energy, and failure mode.
  • the following method was used, based on ASTM F-2029, to prepare the films for the seal experiments: the produced films were conditioned under controlled temperature and humidity (23 ⁇ 2°C and 50 ⁇ 5% relative humidity) for at least 48 hours before seal preparation. Film samples were cut out from the film role in the machine direction to the dimensions 250 mm x 30 mm. The prepared 30mm wide film samples were folded in the long direction with the sealing layers facing each other. For the reported results, the film samples were folded so that the outside bubble skin layers of the film touched each other to be sealed. The prepared sealing sample was further covered with a Teflon sheet in order to prevent the film from adhering to the sealing bars.
  • the whole construction was submitted to a heat sealing with heated sealing bars at the desired seal temperature with a pressure of 0.5 N/mm 2 for 0.5 seconds over a sealing width of 5 mm and cooled down under normal room temperature conditions.
  • the seal temperature was set at 180°C.
  • the seal bar touched the film sample at least 1 cm away from the edge of the film.
  • the formed sealed area had the dimensions of 30 mm x 5 mm.
  • the folded and sealed film sample was then cut at the fold.
  • the sealed samples were conditioned under controlled temperature and humidity (23 ⁇ 2°C and 50 ⁇ 5% relative humidity) for at least 48 hours before the actual seal rupture testing.
  • the conditioned sealed 30 mm wide film samples were further cut to 15 mm width by cutting away the left and right sides of the samples, keeping only the middle part of the sample.
  • the samples were then submitted to tensile testing on an instrumented tensile bench. The speed of the tensile test was set at 500 mm/sec. A minimum amount of 5 samples was measured to test the Energy at Break (or Seal Energy) per film sample. All properties utilized for the evaluation of the failure mode are reported in Table 3. The average of the measured values is reported and a failure mode for each sample is provided.
  • a Failure Mode of "Peeling without Elongation” means the force at maximum was medium, the force at break was low, the elongation at the force at max was low, and the elongation at break was low.
  • a Failure Mode of "Delamination without Elongation” means the force at maximum was high, the force at break was low, the elongation at the force at max was low, and the elongation at break was low.
  • a Failure Mode of "Delamination with Elongation” means the force at maximum was high, the force at break was low, the elongation at the force at max was low, and the elongation at break was high.
  • a Failure Mode of "Elongation with Peeling” means the force at maximum was high, the force at break was low, the elongation at the force at max was high, and the elongation at break was high.
  • a Failure Mode of "Elongation with Delamination” means the force at maximum was high, the force at break was low, the elongation at the force at max was high, and the elongation at break was high.
  • a Failure Mode of "Elongation with Edge Break” means the force at maximum was high, the force at break was high, the elongation at the force at max was high, and the elongation at break was high.
  • Films 6 and 7 having inventive dual reactor blend polymer compositions in the subskin layers show favorably high seal energies (high force and high elongation).
  • Comparative films 4 and 5, produced with single reactor polymers, show poor seal energies (relatively high force with low elongation).
  • the subskin in these films is not functioning as a compatibilizer or tie layer due to the use of only a single component resulting in poor seal energy.
  • the phrases “substantially no,” and “substantially free of are intended to mean that the subject item is not intentionally used or added in any amount, but may be present in very small amounts existing as impurities resulting from environmental or process conditions.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

L'invention concerne un polymère comprenant de 65 % en poids à 90 % en poids, sur la base du poids total du mélange, d'un élastomère d'éthylène-α-oléfine présentant soit une cristallinité nulle, soit une cristallinité dérivée de l'éthylène, ayant plus de 75 % en poids d'unités dérivées de l'éthylène ; et de 10 % en poids à 35 % en poids, sur la base du poids total du mélange, d'un polymère de propylène ayant 40 % en poids ou plus d'unités dérivées du propylène, comprenant des séquences dérivées de propylène disposées de manière isotactique ; l'élastomère d'éthylène-α-oléfine et le polymère de propylène étant préparés dans des réacteurs séparés agencés en configuration parallèle.
PCT/US2017/018285 2016-03-31 2017-02-17 Compositions polymères faiblement cristallines préparées dans un réacteur double WO2017172102A1 (fr)

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SG11201807680TA SG11201807680TA (en) 2016-03-31 2017-02-17 Low crystalline polymer compositions prepared in a dual reactor
CN201780018407.9A CN108779305B (zh) 2016-03-31 2017-02-17 在双反应器中制备的低结晶聚合物组合物
EP17709516.3A EP3436521B1 (fr) 2016-03-31 2017-02-17 Compositions polymères faiblement cristallines préparées dans un double réacteur
CA3018952A CA3018952C (fr) 2016-03-31 2017-02-17 Compositions polymeres faiblement cristallines preparees dans un reacteur double
ES17709516T ES2908980T3 (es) 2016-03-31 2017-02-17 Composiciones poliméricas de baja cristalinidad preparadas en un reactor doble
JP2018551368A JP6990661B2 (ja) 2016-03-31 2017-02-17 ２基リアクターで調製された低結晶性ポリマー組成物

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JP2021509689A (ja) * 2017-12-26 2021-04-01 ダウ グローバル テクノロジーズ エルエルシー マルチモーダルエチレン系ポリマーの製造のための二重反応器溶液プロセス
US11603452B2 (en) 2017-12-26 2023-03-14 Dow Global Technologies Llc Multimodal ethylene-based polymer compositions having improved toughness
US11680119B2 (en) 2017-12-26 2023-06-20 Dow Global Technologies Llc Process for the production of multimodal ethylene-based polymers

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Publication number Priority date Publication date Assignee Title
JP2021509689A (ja) * 2017-12-26 2021-04-01 ダウ グローバル テクノロジーズ エルエルシー マルチモーダルエチレン系ポリマーの製造のための二重反応器溶液プロセス
US11603452B2 (en) 2017-12-26 2023-03-14 Dow Global Technologies Llc Multimodal ethylene-based polymer compositions having improved toughness
US11680119B2 (en) 2017-12-26 2023-06-20 Dow Global Technologies Llc Process for the production of multimodal ethylene-based polymers
US11680120B2 (en) 2017-12-26 2023-06-20 Dow Global Technologies Llc Dual reactor solution process for the production of multimodal ethylene-based polymer
JP7326283B2 (ja) 2017-12-26 2023-08-15 ダウ グローバル テクノロジーズ エルエルシー マルチモーダルエチレン系ポリマーの製造のための二重反応器溶液プロセス

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