WO2020205311A1 - Produit polymère à large distribution de poids moléculaire issu de réacteurs en boucle à gradients thermiques intentionnels - Google Patents

Produit polymère à large distribution de poids moléculaire issu de réacteurs en boucle à gradients thermiques intentionnels Download PDF

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Publication number
WO2020205311A1
WO2020205311A1 PCT/US2020/024226 US2020024226W WO2020205311A1 WO 2020205311 A1 WO2020205311 A1 WO 2020205311A1 US 2020024226 W US2020024226 W US 2020024226W WO 2020205311 A1 WO2020205311 A1 WO 2020205311A1
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Prior art keywords
loop reactor
monomers
loop
psi
methylpentene
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PCT/US2020/024226
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English (en)
Inventor
Yifeng Hong
Jay L. Reimers
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Exxonmobil Chemical Patents Inc.
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Priority to SG11202110446QA priority Critical patent/SG11202110446QA/en
Priority to CN202080025947.1A priority patent/CN113646343A/zh
Priority to EP20720578.2A priority patent/EP3947480A1/fr
Publication of WO2020205311A1 publication Critical patent/WO2020205311A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2400/00—Characteristics for processes of polymerization
    • C08F2400/02—Control or adjustment of polymerization parameters

Definitions

  • the present invention relates to controlling the molecular weight distribution of a polymer product from a polymerization reaction.
  • solution polymerization and slurry polymerization are two major processes that involve dissolution or suspension of polymers in solvent.
  • the monomer, catalyst/activator, and polymer are dissolved into the solvent, typically a nonreactive solvent.
  • Heat released by the reaction is absorbed by the solvent and removed by various methods including, but not limited to, chilling the feed solvent, reflux cooling, jacketed cooling, and external heat exchangers.
  • the solvent and unreacted monomers are flashed off from the polymers in the concentration and devolatilization stages after the reaction.
  • the resulting molten polymers are then extruded and pelletized in water to form small pellets, which are dried and bagged sequentially.
  • Slurry polymerization has similar steps with the major differences being that the polymers are suspended in the solvent and the solvent may be reactive.
  • CSTR Continuous stirred-tank reactor
  • loop reactors are used in both solution and slurry polymerization processes.
  • CSTR solution or slurry polymerization processes beneficially mix the reactants and catalyst well, the processes struggle to accommodate very high heat of polymerization because of inefficient heat removal from the reactor. That is, reflux cooling, cooling jacket, or chilled feed for polymerization in a CSTR provide limited capability of heat removal, which results in higher reaction temperatures.
  • metallocene catalysts are widely used in producing polyolefins because of their higher catalyst activity as compared to conventional Ziegler-Natta catalysts.
  • metallocene catalysts generally require lower reaction temperatures than the Ziegler catalysts. Therefore, a dilute polymer concentration or reduced conversion is usually needed if a CSTR is used in solution or slurry polymerization processes.
  • the loop reactor can overcome the limitations of the CSTR in solution and slurry polymerization processes.
  • loop reactors are several heat exchangers in a loop.
  • the loop reactor can take away massive heat released by the polymerization reactions, which enables high polymer concentration and high monomer conversion.
  • the temperature of reaction can be maintained at considerably lower temperatures than that in CSTR process, meeting the requirement for metallocene catalysts.
  • the present invention relates to broadening the molecular weight distribution of a polymer product from a polymerization reaction by inducing thermal gradients within a loop reactor.
  • a first nonlimiting example embodiment is a method comprising: polymerizing one or more monomers in the presence of a catalyst system in a loop reactor to produce a polyolefin product having a polydispersity index of 2.5 to 8, wherein the loop reactor comprises two or more reactors in series, and wherein the loop reactor has a loop thermal gradient of 50°C to 150°C.
  • a second nonlimiting example embodiment is a method comprising: polymerizing one or more monomers in the presence of a catalyst system in a loop reactor to produce a polyolefin product having a polydispersity index of 2.5 to 8, wherein the loop reactor comprises two or more reactors in series, and wherein the loop reactor has a standard deviation of inter component thermal gradients along the loop reactor of 10°C to 50°C.
  • FIG. 1 illustrates a diagram of an example loop reactor.
  • FIG. 2 illustrates a diagram of an example loop reactor in which different thermal gradients were simulated.
  • FIG. 3 illustrates simulated molecular weight distribution for polymers produced according to simulated polymerization processes including different thermal gradients.
  • the present invention relates to broadening the molecular weight of a polymer product (e.g., polyethylene, polypropylene, etc.) from a polymerization reaction by inducing thermal gradients within in a loop reactor.
  • a polymer product e.g., polyethylene, polypropylene, etc.
  • thermal gradients can be for the overall loop reactor or between components within the loop reactor.
  • an intentionally broadened distribution polymer can simultaneously provide reasonable processability and produce an article with good mechanical properties. Therefore, the ability to control the molecular weight distribution of a polymer product produced in a loop reactor can be very beneficial.
  • a polydispersity index is used herein to characterize the molecular weight distribution.
  • PDI refers to the weight average molecular weight (Mw) divided by the number average molecular weight (Mn). Unless otherwise noted, all molecular weight units (e.g., Mw, Mn) are g/mol, and PDI is unitless.
  • Molecular weights and PDI are determined by Gel Permeation Chromatography (GPC) as described in U.S. Patent Application Publication No. 2006/0173123, which is incorporated herein by reference.
  • FIG. 1 illustrates a diagram of a loop reactor 100.
  • Feedstock comprising one or more monomers is introduced to a first section of loop line 104a of the loop reactor 100 via feedstock line 102.
  • a pump 106 moves material (e.g., feedstock and product) through other components of the loop reactor 100.
  • Components of a loop reactor include, but are not limited to, reactors (e.g., heat exchangers), lines that fluidly connect two reactors, adjacent lines where a polymer product outlet defines a connection point between the adjacent lines, compressors, pumps, and the like.
  • the loop reactor 100 should include two or more reactors.
  • the loop reactor 100 comprises pump 106, m number of sections of loop lines 104a-m, and n number of reactors 108a-n, where m and n can independently be 2 to 50 or more, or 2 to 20, or 2 to 12.
  • the flow A encounters the following components in order: the first section of loop line 104a, a first reactor 108a, second section of loop line 104b, a second reactor 108b, a third section of loop line 104c, a fourth section of loop line 104d, and so on until a m th -l section of loop line 104m-l, a n* reactor 108n, a m th section of loop line 104m, and pump 106 where the flow A completes the loop back into the first section of loop line 104a.
  • a product line 110 that extends from and defines the demarcation between the third section of loop line 104c and the fourth section of loop line 104d.
  • a portion of the material B flowing through the loop reactor 100 can be removed from the loop via the product line 100.
  • the product line 110 and pump 106 can be in other locations along the loop reactor.
  • Catalyst systems can be injected to the loop reactor 100 with the feedstock or at additional ports (not illustrated) along the loop.
  • a“catalyst system” is the combination of at least one catalyst compound, at least one activator, and an optional co activator.
  • the choice of catalyst system(s) depends on the temperature of the reactors 108a- 108n, the chemical composition the monomer(s), the concentration of monomer(s), and the like.
  • the temperature of a component of the loop reactor is the temperature of the material in the component at the outlet of the component.
  • the term“inter-component thermal gradient” is the temperature difference between two adjacent components of a loop reactor.
  • the term“loop thermal gradient” or“loop AT” is the difference between the maximum temperature in the loop reactor and the minimum temperature in the loop reactor. Typically, this is at or near the feedstock entrance. That is, the temperature of the feedstock is low and as the material proceeds around the loop, the temperature increases and is at its max near the feedstock inlet. The cooled feedstock reduces the material to its lowest temperature and the cycle continues. However, chillers or other components could be included to reduce the temperature before the feedstock inlet. Therefore, the loop thermal gradient is referred to an overall maximum temperature minus an overall minimum temperature.
  • the present invention uses reactors operated at different temperatures to create reaction zones that favor the production of different molecular weight polymers, which broadens the molecular weight distribution of the polymer product from the loop reactor.
  • the max DT in the methods and systems of the present invention can be 20°C to 150°C, 50°C to 150°C, or 50°C to 75°C, or 75°C to 125°C, or 100°C to 150°C. Without being limited by theory, it is believed that a higher max DT results in a polymer product with a broader molecular weight distribution (i.e., higher PDI).
  • the standard deviation of the inter-component thermal gradients along the loop reactor in the methods and systems of the present invention can be 10°C to 50°C, or 10°C to 30°C, or 20°C to 40°C, or 25°C to 50°C. Without being limited by theory, it is believed that a higher standard deviation of the inter-component thermal gradients along the loop reactor results in a polymer product with a broader molecular weight distribution (i.e., higher PDI).
  • the polymer product can have a molecular weight distribution with a PDI of 2.2 to 8, 2.5 to 8, or 3 to 6.
  • the methods of the present disclosure can include forming a polyolefin product by polymerizing one or more monomers in the presence of a catalyst system in a loop reactor.
  • the polymerization processes described herein may be carried out in any manner known in the art. Any solution, suspension, slurry, or gas phase polymerization process known in the art can be used. Such processes can be ran in a batch, semi-batch, or continuous mode. Preferably, the polymerization process is continuous.
  • the polymerization process may be a slurry process.
  • the term“slurry polymerization process” means a polymerization process where a supported catalyst is employed and monomers are polymerized on the supported catalyst particles and at least 95 wt% of polymer products derived from the supported catalyst are in granular form as solid particles (not dissolved in the diluent).
  • a slurry polymerization process generally operates between about 1 atmosphere (atm) to about 50 atm pressure (15 psi to 735 psi, 103 kPa to 5068 kPa) or even greater and temperatures in the range of 0°C to about 120°C.
  • a suspension of solid, particulate polymer is formed in a liquid polymerization diluent medium to which monomer and comonomers along with catalyst are added.
  • the suspension including diluent is intermittently or continuously removed from the reactor where the volatile components are separated from the polymer and recycled, optionally after a distillation, to the reactor.
  • the liquid diluent employed in the polymerization medium is typically an alkane having from 3 to 7 carbon atoms, preferably a branched alkane.
  • the medium employed should be liquid under the conditions of polymerization and relatively inert.
  • diluents include, but are not limited to, one methane, ethane, propane, butane, isobutane, isopentane, hexanes, heptanes, and any combination thereof.
  • propane medium the process must be operated above the reaction diluent critical temperature and pressure.
  • a hexane or an isobutane medium is employed.
  • Suitable diluents/solvents for polymerization include non-coordinating, inert liquids.
  • examples include straight and branched-chain hydrocarbons, such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as can be found commercially (ISOPARTM); perhalogenated hydrocarbons, such as perfluorinated C4-10 alkanes, chlorobenzene, and aromatic and alkylsubstituted aromatic compounds, such as benzene, toluene, mesitylene, and xylene.
  • straight and branched-chain hydrocarbons such as isobutane,
  • Suitable solvents also include liquid olefins that may be polymerized including ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-l- pentene, 4-methyl- 1-pentene, 1-octene, 1-decene, and mixtures thereof.
  • aliphatic hydrocarbon solvents are used as the solvent, such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof.
  • the solvent is not aromatic; preferably aromatics are present in the solvent at less than 1 wt%, preferably less than 0.5 wt%, preferably 0 wt % based upon the weight of the solvents.
  • the feedstock concentration of monomers for the polymerization is 60 vol% solvent or less, preferably 40 vol% or less, or preferably 20 vol% or less, based on the total volume of the feedstream.
  • the process may comprise polymerizing one or more monomers dissolved in a solvent as described herein in the presence of a catalyst system under conditions to obtain a first effluent comprising a solution of polyolefin and solvent and/or unreacted monomer.
  • the polymerization processes may be conducted under conditions including a temperature of about 50°C to about 220°C, preferably about 70°C to about 210°C, preferably about 90°C to about 200°C, preferably from 100°C to 190°C, preferably from 130°C to 160°C.
  • the polymerization process may be conducted at a pressure of from about 120 psi to about 1800 psi (about 12,411 kPa), preferably from 200 psi to 1000 psi (about 1379 kPa to 6895 kPa), preferably from 300 psi to 600 psi (about 2068 kPa to 4137 kPa).
  • the pressure is about 450 psi (about 3103 kPa).
  • the feedstock can be introduced at a temperature below reaction temperatures to reduce the concentration of the material in the loop reactor.
  • the feedstock can be introduced, for example, at -10°C to 40°C, preferably from -10°C to 25°C, or preferably from -10°C to 5°C.
  • Hydrogen may be present during the polymerization process at a partial pressure of 0.001 psig to 50 psig (0.007 kPa to 345 kPa), preferably from 0.01 psig to 25 psig (0.07 kPa to 172 kPa), more preferably 0.1 psig to 10 psig (0.7 kPa to 70 kPa).
  • Catalyst systems suitable for use in conjunction with the methods and systems of the present invention can preferably comprise metallocene catalysts and other single site catalysts because these catalysts generally produce polymers with narrow molecular weight distribution.
  • the PDI values for polymers made with metallocene catalyst systems in homogeneous polymerization media are typically close to the statistically expected value of 2.0.
  • any polymerization catalyst capable of polymerizing the monomers disclosed can be used if the catalyst is sufficiently active under the polymerization conditions disclosed herein.
  • Group 3-10 transition metals can form suitable polymerization catalysts.
  • a suitable olefin polymerization catalyst will be able to coordinate to, or otherwise associate with, an alkenyl unsaturation.
  • Examples of olefin polymerization catalysts can include, but are not limited to, Ziegler-Natta catalyst compounds, metallocene catalyst compounds, late transition metal catalyst compounds, and other non-metallocene catalyst compounds.
  • Ziegler-Natta catalysts are those referred to as first, second, third, fourth, and fifth generation catalysts in the Propylene Handbook, E. P. Moore, Jr., Ed., Hanser, New York, 1996.
  • Metallocene catalysts in the same reference are described as sixth generation catalysts.
  • One exemplary non-metallocene catalyst compound comprises non metallocene metal-centered, heteroaryl ligand catalyst compounds (where the metal is chosen from the Group 4, 5, 6, the lanthanide series, or the actinide series of the Periodic Table of the Elements).
  • Non-metallocene metal-centered, heteroaryl ligand catalyst compounds are typically made fresh by mixing a catalyst precursor compound with one or more activators.
  • Non-metallocene metal-centered, heteroaryl ligand catalyst compounds are described in detail in PCT Patent Publications Nos. WO 02/38628, WO 03/040095 (pages 21 to 51), WO 03/040201 (pages 31 to 65), WO 03/040233 (pages 23 to 52), WO 03/040442 (pages 21 to 54), WO 2006/38628, and U.S. Patent Application Publication No. 2008/0153997, each of which is herein incorporated by reference.
  • Activators and associated activation methods can be used in the catalyst system.
  • activators include, but are not limited to, aluminoxane and aluminum alkyl activators, ionizing activators, and nonionizing activators.
  • Examples of ionizing activators and associated methods can be found in European Patent and Application Publication Nos. EP 0570982 A, EP 0520732 A, EP 0495375 A, EP 0500944 Bl, EP 0277003 A and EP 0277004 A; and U.S. Pat. Nos. 5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,384,299, and 5,502,124.
  • Any monomer having one or more (non-conjugated) aliphatic double bond(s) and two or more carbon atoms may be used.
  • monomers include, but are not limited to, a-olefins (e.g., ethylene, propylene, butene-1, hexene-1, octene-1, decene-1, and dodecene- 1), substituted olefins (e.g., styrene, paramethylstyrene, and vinylcyclohexane), non- conjugated dienes (e.g., vinylcyclohexene), a, co-dienes (e.g., 1,5-hexadiene and 1,7-octadiene), cycloolefins (e.g., cyclopentene, cyclohexene, and cyclohexadiene), norbornene, and the like, and any combination thereof.
  • Olefin monomer or monomers can be used.
  • Advantageous monomers include C2 to Cioo olefins, advantageously C2 to C60 olefins, advantageously C3 to C40 olefins advantageously C3 to C20 olefins, advantageously C3 to C12 olefins.
  • Monomers include linear, branched or cyclic alpha-olefins, advantageously C 3 to C 100 alpha-olefins, advantageously C 3 to C 60 alpha- olefins, advantageously C 3 to C 40 alpha-olefins advantageously C 3 to C 20 alpha-olefins, advantageously C 3 to C 12 alpha-olefins.
  • Advantageous olefin monomers can be one or more of ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, dodecene, 4- methylpentene- 1 , 3 -methylpentene- 1 , 3 , 5 , 5 -trimethylhexene- 1 , and 5 -ethylnonene- 1.
  • Aromatic-group-containing monomers containing up to 30 carbon atoms can be used. Suitable aromatic-group-containing monomers comprise at least one aromatic structure, advantageously from one to three, more advantageously a phenyl, indenyl, fluorenyl, or naphthyl moiety.
  • the aromatic-group-containing monomer further comprises at least one polymerizable double bond such that after polymerization, the aromatic structure will be pendant from the polymer backbone.
  • the aromatic-group containing monomer can further be substituted with one or more hydrocarbyl groups including but not limited to Ci to C 10 alkyl groups. Additionally, two adjacent substitutions can be joined to form a ring structure.
  • aromatic-group-containing monomers contain at least one aromatic structure appended to a polymerizable olefinic moiety.
  • Particularly advantageous aromatic monomers include styrene, alpha-methylstyrene, para-alkylstyrenes, vinyltoluenes, vinylnaphthalene, allyl benzene, and indene, especially styrene, paramethylstyrene, 4-phenyl-butene- 1 and allylbenzene.
  • Non-aromatic cyclic group containing monomers can be used. These monomers can contain up to 30 carbon atoms. Suitable non-aromatic cyclic group containing monomers advantageously have at least one polymerizable olefinic group that is either pendant on the cyclic structure or is part of the cyclic structure.
  • the cyclic structure can also be further substituted by one or more hydrocarbyl groups such as, but not limited to, Ci to C 10 alkyl groups.
  • Non-aromatic cyclic group containing monomers include vinylcyclohexane, vinylcyclohexene, vinylnorbomene, ethylidene norbomene, cyclopentadiene, cyclopentene, cyclohexene, cyclobutene, vinyladamantad the like.
  • Diolefin monomer(s) can be used.
  • Advantageous diolefin monomers include any hydrocarbon structure, advantageously C4 to C30, having at least two unsaturated bonds, wherein at least two of the unsaturated bonds are readily incorporated into a polymer by either a stereospecific or a non-stereospecific catalyst(s). It is further advantageous that the diolefin monomers be selected from alpha-omega diene monomers (e.g., divinyl monomers). More advantageously, the diolefin monomers are linear divinyl monomers, most advantageously those containing from 4 to 30 carbon atoms.
  • advantageous dienes include butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, particularly advantageous dienes include 1,6-heptadiene, 1,7- octadiene, 1,8-nonadiene, 1,9-decadiene,
  • cyclic dienes include cyclopentadiene, vinylnorbomene, norbomadiene, ethylidene norbomene, divinylbenzene, dicyclopentadiene or higher ring containing diolefins with or without substituents at various ring positions.
  • a first nonlimiting example embodiment is a method comprising: polymerizing one or more monomers in the presence of a catalyst system in a loop reactor to produce a polyolefin product having a polydispersity index of 2.5 to 8, wherein the loop reactor comprises two or more reactors in series, and wherein the loop reactor has a loop thermal gradient of 50°C to 150°C.
  • a second nonlimiting example embodiment is a method comprising: polymerizing one or more monomers in the presence of a catalyst system in a loop reactor to produce a polyolefin product having a polydispersity index of 2.5 to 8, wherein the loop reactor comprises two or more reactors in series, and wherein the loop reactor has a standard deviation of inter component thermal gradients along the loop reactor of 10°C to 50°C.
  • the foregoing embodiments can further include one or more of the following: Element 1 : wherein the one or more monomers comprises a first monomer selected from the group consisting of: ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, dodecene, 4-methylpentene-l,3-methylpentene-l,3,5,5-trimethylhexene-l, and 5- ethylnonene- 1 ; Element 2: Element 1 and wherein the one or more monomers further comprises a second monomer different than the first monomer and selected from the group consisting of: ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, dodecene, 4- methylpentene- 1 , 3 -methylpentene- 1 , 3 , 5 , 5
  • compositions and methods are described herein in terms of“comprising” various components or steps, the compositions and methods can also“consist essentially of’ or“consist of’ the various components and steps.
  • Example 1 A polymerization reaction was simulated for a loop reactor according to FIG. 2 with different thermal gradients (overall and inter-component thermal gradients).
  • the loop reactor 200 of FIG. 2 includes a feedstock line 202 that supplies feedstock to a first section of loop line 204a.
  • the flow A encounters the following components in order: the first section of loop line 204a, a first reactor 208a, second section of loop line 204b, a second reactor 208b, a third section of loop line 204c, a fourth section of loop line 204d where a product line 210 extends from and defines the demarcation between the third section of loop line 204c and the fourth section of loop line 204d, a third reactor 208c, a fifth section of loop line 204e, a fourth reactor 208d, a sixth section of loop line 204f, a pump 206, and competes the loop at the first section of loop line 204a.
  • the simulation software used was Aspen Plus version 8.8 with the Aspen Polymer Module.
  • the thermodynamic method is based on Perturbed-Chain Statistical Association Fluid Theory (PC-SAFT).
  • PC-SAFT Perturbed-Chain Statistical Association Fluid Theory
  • Plug flow reactors were used to simulate the heat exchangers and loop lines in the loop reactor. The heat exchangers were set to be in isothermal mode while the loop lines were treated adiabatically.
  • the reaction simulated in the example was copolymerization of ethylene and propylene. Copolymerization kinetics were obtained from the literature and implemented in the simulator. Therefore, both heat and mass balance and polymer properties, including chemical composition and molecular weight distribution can be accurately modeled. Metallocene catalyst was used in the catalyst system. The weight fraction ratio of ethylene monomer:propylene monomer: solvent was set to be 4.4%:34.7%:60.9%. The feedstock temperature was 5°C, and the recycle ratio in the loop was 5.
  • the recycle ratio is defined as the ratio between the mass flow rate of the reactor effluent recycled A back to a reactor via a loop line 204 to the mass flow rate of the reactor effluent extracted B as polyolefin product from the loop reactor 200 via the product line 210.
  • Table 1 includes the temperature of the components, which as described above is the temperature at the component outlet, and the resultant max AT of the loop reactor, standard deviation of the inter-component thermal gradients of the loop reactor, and PDI of the polymer product.
  • Case 1 is a control where thermal gradients are not intentionally created in the loop reactor. Cases 2 and 3 have intentional thermal gradients where Case 3 has greater intentional thermal gradients than Case 2. As thermal gradients are intentionally included in and increased in degree (e.g., greater max AT and greater standard deviation of the inter-component thermal gradients) the loop reactor the PDI increases, which indicates that the polyolefin product has a broader molecular weight distribution.
  • FIG. 3 is the simulated molecular weight distribution for the three cases, where Case 3 with the largest thermal gradients has the broadest molecular weight distribution.
  • compositions and methods are described in terms of“comprising,”“containing,” or“including” various components or steps, the compositions and methods can also“consist essentially of’ or“consist of’ the various components and steps. All numbers and ranges disclosed above may vary by some amount. Whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within the range is specifically disclosed. In particular, every range of values (of the form,“from about a to about b,” or, equivalently, “from approximately a to b,” or, equivalently, “from approximately a-b”) disclosed herein is to be understood to set forth every number and range encompassed within the broader range of values.

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Abstract

L'invention porte sur un procédé de production d'une polyoléfine présentant une large distribution de poids moléculaire qui peut comprendre : la polymérisation d'un ou de plusieurs monomères en présence d'un système de catalyseur dans un réacteur en boucle pour produire un produit de polyoléfine présentant un indice de polydispersité de 2,5 à 8, le réacteur en boucle comprenant au moins deux réacteurs en série, et le réacteur en boucle présentant un gradient thermique en boucle de 50 °C à 150 °C et/ou un écart type de gradients thermiques entre composants le long du réacteur en boucle de 10 °C à 50° C.
PCT/US2020/024226 2019-04-05 2020-03-23 Produit polymère à large distribution de poids moléculaire issu de réacteurs en boucle à gradients thermiques intentionnels WO2020205311A1 (fr)

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SG11202110446QA SG11202110446QA (en) 2019-04-05 2020-03-23 Broad molecular weight distribution polymer product from loop reactors with intentional thermal gradients
CN202080025947.1A CN113646343A (zh) 2019-04-05 2020-03-23 来自具有故意热梯度的环管反应器的宽分子量分布聚合物产物
EP20720578.2A EP3947480A1 (fr) 2019-04-05 2020-03-23 Produit polymère à large distribution de poids moléculaire issu de réacteurs en boucle à gradients thermiques intentionnels

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