EP3946713A1 - Régulation de la distribution de poids moléculaire et de la distribution de composition chimique d'un produit de polyoléfine - Google Patents

Régulation de la distribution de poids moléculaire et de la distribution de composition chimique d'un produit de polyoléfine

Info

Publication number
EP3946713A1
EP3946713A1 EP20718116.5A EP20718116A EP3946713A1 EP 3946713 A1 EP3946713 A1 EP 3946713A1 EP 20718116 A EP20718116 A EP 20718116A EP 3946713 A1 EP3946713 A1 EP 3946713A1
Authority
EP
European Patent Office
Prior art keywords
polyolefin product
molecular weight
monomers
chemical composition
psi
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20718116.5A
Other languages
German (de)
English (en)
Inventor
Yifeng Hong
Jay L. Reimers
Jun Shi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Chemical Patents Inc
Original Assignee
ExxonMobil Chemical Patents Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ExxonMobil Chemical Patents Inc filed Critical ExxonMobil Chemical Patents Inc
Publication of EP3946713A1 publication Critical patent/EP3946713A1/fr
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • B01J19/2435—Loop-type reactors
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/14—Organic medium
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00076—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements inside the reactor
    • B01J2219/00081—Tubes

Definitions

  • the present invention relates to controlling the molecular weight distribution and chemical composition of a polyolefin 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 can 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 of metallocene catalysts.
  • the present invention relates to controlling the molecular weight distribution and chemical composition of a polyolefin product from a polymerization reaction by controlling the polymerization parameters of recycle ratio, polymer concentration, and/or Loop Reactor Scale-Up Number (“LRSU Number”) number in a loop reactor.
  • LRSU Number Loop Reactor Scale-Up Number
  • a first example embodiment is a method comprising: polymerizing a feedstock in the presence of a metallocene catalyst in a loop reactor to produce a polyolefin product, the feedstock comprising two or more monomers; and broadening a molecular weight distribution and/or broadening a chemical composition distribution of the polyolefin product by adjusting a polymerization parameter selected from the group consisting of decreasing a recycle ratio, increasing a polymer concentration, increasing a LRSU number, and any combination thereof.
  • Another example embodiment is a method comprising: polymerizing a feedstock in the presence of a metallocene catalyst in a loop reactor to produce a polyolefin product, the feedstock comprising two or more monomers; and narrowing a molecular weight distribution and/or narrowing a chemical composition distribution of the polyolefin product by adjusting a polymerization parameter selected from the group consisting of increasing a recycle ratio, decreasing a polymer concentration, decreasing a LRSU number, and any combination thereof.
  • FIG. 1 illustrates a diagram of a loop reactor.
  • FIG. 2 is the polydispersity index (PDI) as a function of recycle ratio and polymer concentration for the polyolefin product of a first simulated polymerization process.
  • FIG. 3 is the percent change of ethylene content (%AC2) as a function of recycle ratio and polymer concentration for the polyolefin product of a first simulated polymerization process.
  • FIG. 4 is the PDI as a function of a LRSU number (LRSU) for the polyolefin product of a second simulated polymerization process.
  • LRSU LRSU number
  • FIG. 5 is the %AC2 as a function of LRSU number for the polyolefin product of a second simulated polymerization process.
  • the present invention relates to controlling the molecular weight distribution and chemical composition distribution of a polyolefin product from a polymerization reaction by controlling the polymerization parameters of recycle ratio, polymer concentration, and/or LRSU number in a loop reactor.
  • a narrow distribution for both the molecular weight and chemical composition is desired, sometimes 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 and chemical composition distribution of a polyolefin 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.
  • GPC Gel Permeation Chromatography
  • a percent change of monomer content is used herein to characterize the chemical composition distribution, where Cx defines the monomer.
  • the %ACx is the standard deviation of the Cx weight fraction in the polyolefin product divided by the mean Cx weight fraction in the polyolefin product times 100.
  • the Cx weight fraction in the polyolefin product and the corresponding standard deviation and mean are determined by Temperature Rising Elation Fraction (TREF), as described in Wild, et al., J. Poly. Sci, Poly. Phys. Ed., vol. 20, p. 441 (1982), which is incorporated herein by reference.
  • TREF Temperature Rising Elation Fraction
  • the polyolefin is a copolymer of two monomers
  • the %ACx for each is the same, so either monomer can be referenced when describing the chemical composition distribution of the polyolefin product.
  • the polyolefin is a copolymer of three or more monomers, the greatest %ACx is used to characterize the chemical composition distribution of the polyolefin product.
  • a“catalyst system” is the combination of at least one catalyst compound, at least one activator, and an optional co-activator.
  • the“polymer concentration” of a loop reactor is a weight percent of polymer relative to the polymer-monomer total weight. Unless otherwise specified, the polymer concentration is measured at the effluent of the heat exchanger.
  • the term“polymer concentration gradient” of a loop reactor is the polymer concentration at the effluent of the heat exchanger minus the polymer concentration at the inlet of the heat exchanger.
  • the term“temperature gradient” is the temperature at the effluent of the heat exchanger minus the temperature at the inlet of the heat exchanger.
  • FIG. 1 illustrates a diagram of a loop reactor 100.
  • Feedstock comprising two or more monomers is introduced to the loop line 104 of the loop reactor 100 via feedstock line 102.
  • a pump 106 and a reactor 108 are in series along the loop line 104.
  • a product line 110 where polyolefin product is removed from the loop reactor 100.
  • the polyolefin product from the loop reactor 100 can be further treated, for example, with a devolatilization step.
  • only one reactor 108 is shown.
  • a loop reactor can include more than one reactor 108 in series.
  • One or more catalyst systems can be used in conjunction with the loop reactor 100. Catalyst systems can be injected to the loop reactor 100 with the feedstock or at additional ports (not illustrated) along the loop.
  • the reactor 108 comprises a heat exchanger used to control the temperature of the polymerization reaction. As described above, heat released by the polymerization reaction is absorbed by the solvent and removed by the heat exchanger.
  • the recycle ratio is defined as the ratio between the mass flow rate of the reactor effluent A recycled back to the reactor via the loop line 104 and the mass flow rate of the reactor effluent B extracted as polyolefin product from the reactor 100 via the product line 110.
  • a high recycle ratio represents a high portion of reactant coming back and mixed with fresh feed and a short residence time in the reactor per pass. Without being limited by theory, it is believed that the short residence time reduces the reactant and temperature gradients in the reactor and produces a product with a narrow molecular weight distribution and a narrow chemical composition distribution.
  • the recycle ratio can vary from 0.1 to 10, or 0.3 to 7, or 0.5 to 6. With all other variables constant, a lower recycle ratio (e.g., 0.1 to 1) can produce polyolefin product with a broader molecular weight distribution and a broader chemical composition distribution. Conversely, with all other variables constant, a higher recycle ratio (e.g., 2 or greater) can be used to produce a polyolefin product with a more narrow molecular weight distribution and a more narrow chemical composition distribution.
  • the polymer concentration is controlled by the catalyst reaction rate and the heat removed from the reactor (e.g., from the heat exchanger and feed chilling). Without being limited by theory, with a constant feed rate, a low polymer concentration can be attributed to a lower polymerization rate that results in lower temperature gradients and lower monomer concentration gradients across the reactor.
  • the polymer concentration can vary from 5 wt% to 50 wt%, or 10 wt % to 25 wt%. With all other variables constant, a lower polymer concentration (e.g., less than 15 wt%) can produce polyolefin product with a more narrow molecular weight distribution and a more narrow chemical composition distribution. Conversely, with all other variables constant, a higher polymer concentration (e.g., 15 wt% or greater) can be used to produce a polyolefin product with a broader molecular weight distribution and a broader chemical composition distribution.
  • a Damkohler number (Da) is a dimensionless number used in chemical engineering that relates reaction rate to transport rate. In its most commonly used form, the Damkohler number relates the reaction timescale to the convection time scale, volumetric flow rate, through the reactor for continuous (plug flow or stirred tank) or semibatch chemical processes according to Eq. 1. reaction rate bombard .
  • the inventors have created a dimensionless parameter based on the Damkohler number that describes a polymerization process within a loop reactor, the Loop Reactor Scale- Up (“LRSU”) number. Because the LRSU number is dimensionless, for a given reaction, it is constant between small scale loop reactors, such as that used in a pilot polymerization plant, and large scale reactors, such as that used in a commercial polymerization plant. In a loop polymerization process, the order of the reaction can be considered to be second-order. The LRSU number can be calculated by Eq.
  • LRSU represents the LRSU number
  • t is the residence time
  • k p is the polymerization rate constant of major monomer which is also a function of temperature
  • C mon is the major monomer concentration (i.e., and C c * at is the reciprocal of catalyst activity.
  • major monomer refers to the monomer having the highest weight concentration in the feedstock.
  • a small LRSU number can reduce the temperature gradient and monomer concentration gradient in the loop reactor, which leads to narrow chemical composition and molecular weight distribution.
  • the LRSU number can vary from 0.1 to 100, or 0.5 to 85. With all other variables constant, a lower LRSU number (e.g., less than 10) can produce polyolefin product with a narrower molecular weight distribution and a narrower chemical composition distribution. Conversely, with all other variables constant, a higher LRSU number (e.g., 15 or greater) can be used to produce a polyolefin product with a broader molecular weight distribution and a broader chemical composition distribution. [0035] One or more of the three polymerization parameters (recycle ratio, polymer concentration, and/or LRSU number) can be used to control the molecular weight distribution and/or the chemical composition distribution.
  • a lower recycle rate and higher polymer concentration together can broaden the molecular weight distribution and broaden chemical composition distribution.
  • the molecular weight distribution and chemical composition distribution may both still be reasonably broad but less broad than the foregoing case. Therefore, the three polymerization parameters can be used in tandem to dial in a desired molecular weight distribution and chemical composition distribution to achieve a balance in polymer melt processability and product mechanical properties.
  • the polyolefin product can have a molecular weight distribution with a PDI of 1.5 to 8, or 2 to 6.
  • the PDI may preferably be 3 or greater, or 3 to 8, or 3 to 6.
  • one or more of the three polymerization parameters described herein can be adjusted to achieve the broad molecular weight distribution.
  • the polyolefin product can have a chemical composition distribution with a %AC2 of 0.5% to 50%, or 1% to 45%.
  • the %AC2 may preferably be 15% or greater, or 15% to 50%, or 20% to 45%.
  • one or more of the three polymerization parameters described herein can be adjusted to achieve the broad chemical composition distribution.
  • the methods of the present disclosure can include forming a polyolefin product by polymerizing two 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 that can 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 polymerization process may be a solution polymerization.
  • the process may comprise polymerizing two 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).
  • 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 a catalyst system.
  • activators include, but are not limited to, aluminoxane and aluminum alkyl activators, ionizing activators, and nonionizing activators.
  • EP 0 570 982 A examples of ionizing activators and associated methods can be found in European Patent and Application Publication Nos. EP 0 570 982 A, EP 0 520 732 A, EP 0 495 375 A, EP 0 500 944 Bl, EP 0 277 003 A and EP 0 277 004 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 C 2 to Cioo olefins, advantageously C 2 to Ceo olefins, advantageously C 3 to C 40 olefins advantageously C 3 to C 20 olefins, advantageously C 3 to C 12 olefins.
  • Monomers can include linear, branched or cyclic alpha-olefins, advantageously C 3 to Cioo 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 and the like.
  • Diolefin monomer(s) can be used.
  • Advantageous diolefin monomers include any hydrocarbon structure, advantageously C 4 to C 30 , 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 example embodiment is a method comprising: polymerizing a feedstock in the presence of a metallocene catalyst in a loop reactor to produce a polyolefin product, the feedstock comprising two or more monomers; and broadening a molecular weight distribution and/or broadening a chemical composition distribution of the polyolefin product by adjusting a polymerization parameter selected from the group consisting of decreasing a recycle ratio, increasing a polymer concentration, increasing a LRSU number, and any combination thereof.
  • this method can further include one or more of the following: Element 1: wherein the a first of the two or more monomers is 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-l; Element 2: Element 1 and wherein a second of the two or more monomers is different than the first and is 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-1, 5-ethylnonene-l
  • Element 1 and optionally Element 2 in combination with one or more of Elements 3-5 and optionally in further combination with Element 6 or 7; Element 1 and optionally Element 2 in combination with Element 6 or 7; one or more of Elements 3-5 in combination with Element 6 or 7; and two or more of Elements 3-5 in combination.
  • Another example embodiment is a method comprising: polymerizing a feedstock in the presence of a metallocene catalyst in a loop reactor to produce a polyolefin product, the feedstock comprising two or more monomers; and narrowing a molecular weight distribution and/or narrowing a chemical composition distribution of the polyolefin product by adjusting a polymerization parameter selected from the group consisting of increasing a recycle ratio, decreasing a polymer concentration, decreasing a LRSU number, and any combination thereof.
  • this method can further include one or more of the following: Element 1; Element 2; Element 6; Element 7; Element 8: wherein the molecular weight distribution as measured by polydispersity index of the polyolefin product is less than 3; Element 9: wherein the chemical composition distribution as measured by percent change of monomer content of the polyolefin product is less than 15%; and Element 10: wherein after adjusting the polymerization parameter the recycle ratio is greater than 1, the polymer concentration is less than 15 wt%, and/or the LRSU number is less than 15.
  • Examples of combinations of the foregoing include, but are not limited to, Element 1 and optionally Element 2 in combination with one or more of Elements 8-10 and optionally in further combination with Element 6 or 7; Element 1 and optionally Element 2 in combination with Element 6 or 7; one or more of Elements 8-10 in combination with Element 6 or 7; and two or more of Elements 8-10 in combination.
  • 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 with varied polymerization parameters of recycle ratio and polymer concentration.
  • 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.
  • a metallocene catalyst was used in the catalyst system.
  • the weight fraction ratio of ethylene monomer:propylene monomer: solvent was set to be 3.8%:35.4%:60.8%.
  • the feedstock temperature was 5°C.
  • the molecular weight distribution was characterized by the polydispersity (PDI).
  • the chemical composition distribution is characterized by the %AC2.
  • FIG. 2 is the PDI as a function of recycle ratio and polymer concentration.
  • FIG. 3 is the %AC2 as a function of recycle ratio and polymer concentration. In both FIGS. 2 and 3, the size of the bubble in the plot corresponds to relative polymer concentration.
  • Table 1 is the data represented in the figures.
  • This example illustrates that reducing the recycle ratio and increasing the polymer concentration (individually or together) can be used to broaden the molecular weight distribution and/or broaden the chemical composition distribution. Conversely, increasing the recycle ratio and decreasing the polymer concentration (individually or together) can be used to narrow the molecular weight distribution and/or narrow the chemical composition distribution.
  • Example 2 A polymerization reaction was simulated with varied polymerization parameter values for the Loop Reactor Scale-Up number (LRSU). As with Example 1, the simulation software used was Aspen Plus version 8.8 with the Aspen Polymer Module except the weight fraction ratio of ethylene monomerpropylene monomer: solvent was set to be 4.2%:33.7%:62.1%. Because propylene is the major monomer in the feedstock, the LRSU is based on propylene. The LRSU number was adjusted between 0.55 and 81.05. LIG. 4 is the PDI as a function of Da. LIG. 5 is the %AC2 as a function of Da. Table 2 is the data represented in the figures.
  • LRSU Loop Reactor Scale-Up number
  • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Un procédé d'élargissement d'une distribution de poids moléculaire et/ou d'élargissement d'une distribution de composition chimique du produit de polyoléfine peut comprendre : la polymérisation d'une charge d'alimentation en présence d'un catalyseur métallocène dans un réacteur à boucle pour produire un produit de polyoléfine, la charge d'alimentation comprenant deux monomères ou plus; et l'ajustement d'un paramètre de polymérisation choisi dans le groupe constitué par la réduction d'un rapport de recyclage, l'augmentation d'une concentration de polymère, l'augmentation d'un nombre LRSU, et toute combinaison de celles-ci.
EP20718116.5A 2019-04-05 2020-03-24 Régulation de la distribution de poids moléculaire et de la distribution de composition chimique d'un produit de polyoléfine Pending EP3946713A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US201962829871P 2019-04-05 2019-04-05
EP19173841 2019-05-10
PCT/US2020/024449 WO2020205337A1 (fr) 2019-04-05 2020-03-24 Régulation de la distribution de poids moléculaire et de la distribution de composition chimique d'un produit de polyoléfine

Publications (1)

Publication Number Publication Date
EP3946713A1 true EP3946713A1 (fr) 2022-02-09

Family

ID=70228893

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20718116.5A Pending EP3946713A1 (fr) 2019-04-05 2020-03-24 Régulation de la distribution de poids moléculaire et de la distribution de composition chimique d'un produit de polyoléfine

Country Status (4)

Country Link
EP (1) EP3946713A1 (fr)
CN (1) CN113646074B (fr)
SG (1) SG11202110447SA (fr)
WO (1) WO2020205337A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112430282B (zh) * 2020-11-18 2022-06-17 浙江大学 一种低熔融指数的聚烯烃及其应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997036942A1 (fr) * 1996-04-01 1997-10-09 The Dow Chemical Company Polymerisation en solution d'olefines
WO2006101597A1 (fr) * 2005-03-17 2006-09-28 Dow Global Technologies Inc. Copolymeres pseudo-sequences et procede comprenant l'utilisation d'un agent de transfert de chaines
US20100160579A1 (en) * 2008-12-18 2010-06-24 Chevron Phillips Chemical Company Lp Process for producing broader molecular weight distribution polymers with a reverse comonomer distribution and low levels of long chain branches
US9493589B1 (en) * 2015-09-09 2016-11-15 Chevron Phillips Chemical Company Lp Polymers with improved ESCR for blow molding applications

Family Cites Families (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4665208A (en) 1985-07-11 1987-05-12 Exxon Chemical Patents Inc. Process for the preparation of alumoxanes
EP0594218B1 (fr) 1986-09-24 1999-03-17 Mitsui Chemicals, Inc. Procédé de polymérisation d'oléfines
JPH0780933B2 (ja) 1986-11-20 1995-08-30 三井石油化学工業株式会社 オレフインの重合方法
US5241025A (en) 1987-01-30 1993-08-31 Exxon Chemical Patents Inc. Catalyst system of enhanced productivity
US5384299A (en) 1987-01-30 1995-01-24 Exxon Chemical Patents Inc. Ionic metallocene catalyst compositions
IL85097A (en) 1987-01-30 1992-02-16 Exxon Chemical Patents Inc Catalysts based on derivatives of a bis(cyclopentadienyl)group ivb metal compound,their preparation and their use in polymerization processes
US5153157A (en) 1987-01-30 1992-10-06 Exxon Chemical Patents Inc. Catalyst system of enhanced productivity
US5198401A (en) 1987-01-30 1993-03-30 Exxon Chemical Patents Inc. Ionic metallocene catalyst compositions
PL276385A1 (en) 1987-01-30 1989-07-24 Exxon Chemical Patents Inc Method for polymerization of olefines,diolefins and acetylene unsaturated compounds
JPH0742301B2 (ja) 1987-02-14 1995-05-10 三井石油化学工業株式会社 微粒子状アルミノオキサン、その製法およびその用途
JP2538588B2 (ja) 1987-04-03 1996-09-25 三井石油化学工業株式会社 オレフイン重合用固体触媒の製法
US5206199A (en) 1987-04-20 1993-04-27 Mitsui Petrochemical Industries, Ltd. Catalyst for polymerizing an olefin and process for polymerizing an olefin
US5091352A (en) 1988-09-14 1992-02-25 Mitsui Petrochemical Industries, Ltd. Olefin polymerization catalyst component, olefin polymerization catalyst and process for the polymerization of olefins
US5041584A (en) 1988-12-02 1991-08-20 Texas Alkyls, Inc. Modified methylaluminoxane
US4908463A (en) 1988-12-05 1990-03-13 Ethyl Corporation Aluminoxane process
US5103031A (en) 1989-02-21 1992-04-07 Ethyl Corporation Falling film aluminoxane process
US4968827A (en) 1989-06-06 1990-11-06 Ethyl Corporation Alkylaluminoxane process
US4924018A (en) 1989-06-26 1990-05-08 Ethyl Corporation Alkylaluminoxane process
US5066741A (en) 1990-03-22 1991-11-19 The Dow Chemical Company Process for preparation of syndiotactic vinyl aromatic polymers
CA2066247C (fr) 1990-07-24 1998-09-15 Ryuichi Sugimoto Catalyseur de polymerisation pour .alpha.-olefines et methode pour preparer des poly-.alpha.-olefines a l'aide de ce catalyseur
US5189192A (en) 1991-01-16 1993-02-23 The Dow Chemical Company Process for preparing addition polymerization catalysts via metal center oxidation
US5206197A (en) 1991-03-04 1993-04-27 The Dow Chemical Company Catalyst composition for preparation of syndiotactic vinyl aromatic polymers
US5341124A (en) 1991-05-29 1994-08-23 Se-Kure Controls, Inc. Mountable product sensor and display stand
US5721185A (en) 1991-06-24 1998-02-24 The Dow Chemical Company Homogeneous olefin polymerization catalyst by abstraction with lewis acids
US5235081A (en) 1992-03-18 1993-08-10 Ethyl Corporation Method of removing gel forming materials from methylaluminoxanes
US5157137A (en) 1991-07-26 1992-10-20 Ethyl Corporation Method of making gel free alkylaluminoxane solutions
US5329032A (en) 1992-03-18 1994-07-12 Akzo Chemicals Inc. Polymethylaluminoxane of enhanced solution stability
US5434115A (en) 1992-05-22 1995-07-18 Tosoh Corporation Process for producing olefin polymer
DE69326463T2 (de) 1992-07-01 2000-05-04 Exxon Chemical Patents, Inc. Olefinpolymerisationskatalysatoren auf basis von uebergangsmetallen
US5248801A (en) 1992-08-27 1993-09-28 Ethyl Corporation Preparation of methylaluminoxanes
US5939346A (en) 1992-11-02 1999-08-17 Akzo Nobel N.V. Catalyst system comprising an aryloxyaluminoxane containing an electron withdrawing group
US6727361B2 (en) 2000-11-07 2004-04-27 Symyx Technologies, Inc. Phosphino substituted pyridine amine ligands
CN1500100A (zh) * 2000-12-20 2004-05-26 ����ɭ���ڻ�ѧר����˾ 生产支链聚合物组合物的烯烃聚合方法
DK1453994T3 (da) 2001-11-06 2007-09-10 Dow Global Technologies Inc Isotaktiske propylencopolymerfibre, deres fremstilling og anvendelse
SG147306A1 (en) 2001-11-06 2008-11-28 Dow Global Technologies Inc Isotactic propylene copolymers, their preparation and use
AU2002356914A1 (en) 2001-11-06 2003-05-19 Dow Global Technologies Inc. Crystallization of polypropylene using a semi-crystalline, branched or coupled nucleating agent
WO2003040233A2 (fr) 2001-11-06 2003-05-15 Dow Global Technologies Inc. Melanges polymeres, resistant aux chocs, de polypropylene cristallin et d'agents antichoc de faible poids moleculaire partiellement cristallins
US7795366B2 (en) 2002-08-12 2010-09-14 Exxonmobil Chemical Patents Inc. Modified polyethylene compositions
US20080153997A1 (en) 2006-12-20 2008-06-26 Exxonmobil Research And Engineering Polymer production at supercritical conditions
KR100869995B1 (ko) 2004-10-06 2008-11-24 니폰 덴신 덴와 가부시끼가이샤 혈압계
US8288487B2 (en) * 2010-07-06 2012-10-16 Chevron Phillips Chemical Company Lp Catalysts for producing broad molecular weight distribution polyolefins in the absence of added hydrogen

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997036942A1 (fr) * 1996-04-01 1997-10-09 The Dow Chemical Company Polymerisation en solution d'olefines
WO2006101597A1 (fr) * 2005-03-17 2006-09-28 Dow Global Technologies Inc. Copolymeres pseudo-sequences et procede comprenant l'utilisation d'un agent de transfert de chaines
US20100160579A1 (en) * 2008-12-18 2010-06-24 Chevron Phillips Chemical Company Lp Process for producing broader molecular weight distribution polymers with a reverse comonomer distribution and low levels of long chain branches
US9493589B1 (en) * 2015-09-09 2016-11-15 Chevron Phillips Chemical Company Lp Polymers with improved ESCR for blow molding applications

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
JORGE JARDIM ZACCA ET AL: "MODELLING OF THE LIQUID PHASE POLYMERIZATION OF OLEFINS IN LOOP REACTORS", CHEMICAL ENGINEERING SCIENCE, OXFORD, GB, vol. 48, no. 22, 1 November 1993 (1993-11-01), pages 3743 - 3765, XP008017504, ISSN: 0009-2509, DOI: 10.1016/0009-2509(93)80218-F *
See also references of WO2020205337A1 *
ZHENG-HONG LUO ET AL: "Mathematical modeling of the molecular weight distribution of polypropylene produced in a loop reactor", POLYMER ENGINEERING AND SCIENCE., vol. 47, no. 10, 12 September 2007 (2007-09-12), US, pages 1643 - 1649, XP055625513, ISSN: 0032-3888, DOI: 10.1002/pen.20848 *

Also Published As

Publication number Publication date
CN113646074A (zh) 2021-11-12
SG11202110447SA (en) 2021-10-28
WO2020205337A1 (fr) 2020-10-08
CN113646074B (zh) 2023-05-09

Similar Documents

Publication Publication Date Title
CA2278042C (fr) Catalyseur a base de plusieurs phosphinimines
US11332553B2 (en) Catalyst composition for polymerizing polyolefin, method for producing polyolefin, and polyolefin resin
CN1299377A (zh) 聚合催化剂
US11434309B2 (en) Controlling molecular weight distribution and chemical composition distribution of a polyolefin product
US10718571B2 (en) Spiral heat exchanger as preheater in polymer devolatilization processes
KR102682379B1 (ko) 고용융장력 폴리프로필렌 수지 제조방법
US4621124A (en) Catalyst system for the polymerization of ethylene
EP3946713A1 (fr) Régulation de la distribution de poids moléculaire et de la distribution de composition chimique d'un produit de polyoléfine
EP1448633B2 (fr) Procede de polymerisation en deux etapes
US11492427B2 (en) Production of gradient copolymers using monomer and comonomer concentration gradients in a loop reactor
EP1902079B1 (fr) Procede permettant de retrecir la distribution des ramifications des chaines courtes dans les produits et polymerisations de l'ethylene en deux etapes
US11530279B2 (en) Broad molecular weight distribution polymer product from loop reactors with intentional thermal gradients
US6034192A (en) Germanium bridged metallocenes producing polymers with increased melt strength
EP3947480A1 (fr) Produit polymère à large distribution de poids moléculaire issu de réacteurs en boucle à gradients thermiques intentionnels
CN114945602B (zh) 一种烯烃聚合用催化剂和使用其的聚合方法
US11629214B2 (en) Producing blocks of block copolymer in a separator downstream of a reactor
EP3507310B1 (fr) Échangeur de chaleur spiralé comme préchauffeur dans des processus d'extraction de polymères volatiles
WO2021034471A1 (fr) Production de blocs de copolymère séquencé dans un séparateur en aval d'un réacteur
US11945888B2 (en) Solution polymerization process and product control using effluent density
Debling Modeling particle growth and morphology of impact polypropylene produced in the gas phase
WO2018044395A1 (fr) Échangeur de chaleur spiralé, comme préchauffeur dans des procédés de dévolatilisation de polymères
KR101496383B1 (ko) 에틸렌/알파-올레핀 공중합체의 합성용 촉매 조성물 및 에틸렌/알파-올레핀 공중합체의 제조 방법

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20211015

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20230419