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WO2025216983A1 - Procédé de production de polyéthylènes - Google Patents

Procédé de production de polyéthylènes

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Publication number
WO2025216983A1
WO2025216983A1 PCT/US2025/023154 US2025023154W WO2025216983A1 WO 2025216983 A1 WO2025216983 A1 WO 2025216983A1 US 2025023154 W US2025023154 W US 2025023154W WO 2025216983 A1 WO2025216983 A1 WO 2025216983A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
loop
polymerization
injection point
heat
Prior art date
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Pending
Application number
PCT/US2025/023154
Other languages
English (en)
Inventor
Sean W. Ewart
Yi Jin
Ying Yu
Frederik GEMOETS
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.)
Dow Global Technologies LLC
Original Assignee
Dow Global Technologies LLC
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Filing date
Publication date
Application filed by Dow Global Technologies LLC filed Critical Dow Global Technologies LLC
Publication of WO2025216983A1 publication Critical patent/WO2025216983A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • 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
    • C08F2400/00—Characteristics for processes of polymerization
    • C08F2400/02—Control or adjustment of polymerization parameters
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+

Definitions

  • Embodiments of the present disclosure generally relate to the production of ethylene- based polymers, and more specifically, to the production of ethylene-based polymers in loop reactors.
  • BACKGROUND [0003] When polyethylene copolymers are produced in a loop reactor, the relative concentrations of monomer and comonomer vary around the loop.
  • catalyst half-life may be 50% or less of catalyst recirculation time. This short half-life, relative to recirculation time, is believed to result in excessive catalyst activity in the first half of the loop and insufficient catalyst activity in the second half of the loop, thereby causing an excessively broad short chain branching distribution. Accordingly, processes for the production of ethylene-based polymers that 85922-WO-PCT/DOW 85922 WO mitigate the issues of excessive short chain branching and relatively short catalyst half-life are desired. [0005] Embodiments of the present disclosure meet this need by providing a loop reactor comprising a first catalyst injection point in the first half of the loop and a second catalyst injection point in the second half of the loop.
  • Embodiments then control one or more polymerization conditions (e.g., a ratio of catalyst introduced at the second catalyst injection point to catalyst introduced at the first catalyst injection point) such that a ratio of an amount of polymerization in the first half of the loop to an amount of polymerization in the second half is controlled, such as from 0.7 to 1.3; a ratio of the heat of polymerization in the first half to the heat of polymerization in the second half is from 0.7 to 1.3; or both. Controlling the polymerization conditions is believed to balance polymerization around the reactor, resulting in reduced concentration gradients of monomers and comonomers and a narrower short chain branching distribution.
  • a ratio of catalyst introduced at the second catalyst injection point to catalyst introduced at the first catalyst injection point
  • the polymerization condition which is controlled is a ratio of catalyst injected at the second catalyst injection point to catalyst injected at the first catalyst injection point. Controlling the polymerization by controlling the ratio of catalysts introduced at the two injection points in this manner is believed to be a particularly effective and inexpensive method by which to control polymerization rates.
  • Further embodiments of the present disclosure meet this need by providing loop reactors where the number of catalyst injection points equals the number of feed injection points. Although loop reactors with two feed injection points have been in operation for several decades now and the need to narrow short chain branching distribution has been known, it was not understood that increasing the number of catalyst injection points to equal the number of feed injection points could be a viable way to narrow short chain branching distribution.
  • a process for forming an ethylene-based polymer may comprise: introducing catalyst to a loop reactor through at least two catalyst injection points, where: the loop comprises a first half and a second half, and the first catalyst injection point is in the first half of the loop and the second catalyst injection point is in the second 85922-WO-PCT/DOW 85922 WO half of the loop; and polymerizing the ethylene and copolymer while controlling one or more polymerization conditions such that: a ratio of an amount of polymerization in the first half to an amount of polymerization in the second half is from 0.7 to 1.3; a ratio of the heat of polymerization in the first half to the heat of polymerization in the second half is from 0.7 to 1.3; or both, thereby forming the ethylene-based polymer.
  • FIG. 1 schematically depicts the operation of a loop reactor, according to one or more embodiments described herein; [0012] FIG.
  • FIG. 2 is a HT-TGIC spectra used to determine short chain branching;
  • FIG. 3 is a HT-TGIC spectra for Example 1 and Comparative Example 1;
  • FIG. 4 is a HT-TGIC spectra for Example 2 and Comparative Example 2; and
  • FIG. 5 is a HT-TGIC spectra for Example 3 and Comparative Example 3.
  • polymer refers to a polymeric compound prepared by polymerizing monomers, whether of the same or a different type.
  • the generic term polymer thus embraces the term “homopolymer,” usually employed to refer to polymers prepared from only one type of monomer as well as “copolymer” which refers to polymers prepared from two or more different monomer types.
  • Polyethylene or “ethylene-based polymer” shall mean polymers comprising greater than 50% by weight of units that have been derived from ethylene monomer. This includes polyethylene homopolymers or copolymers (meaning units derived from two or more monomer types).
  • LDPE Low Density Polyethylene
  • LLDPE Linear Low Density Polyethylene
  • ULDPE Ultra Low Density Polyethylene
  • VLDPE Very Low Density Polyethylene
  • m-LLDPE linear low density resins
  • MDPE Medium Density Polyethylene
  • HDPE High Density Polyethylene
  • LDPE low density polymer
  • high pressure ethylene polymer or “highly branched polyethylene” and is defined to mean that the polymer is partly or entirely homopolymerized or copolymerized in autoclave or tubular reactors at pressures above 14,500 psi (100 MPa) with the use of free-radical initiators, such as peroxides (see, for example, U.S. Patent No. 4,599,392, which is hereby incorporated by reference in its entirety).
  • LDPE resins typically have a density in the range of 0.916 g/cm 3 to 0.930 g/cm 3 .
  • LLDPE includes resin made using Ziegler-Natta catalyst systems as well as resin made using single-site catalysts, including, but not limited to, bis-metallocene catalysts (sometimes referred to as “m-LLDPE”), phosphinimine, and constrained geometry catalysts, and resins made using post-metallocene, molecular catalysts, including, but not limited to, bis(biphenylphenoxy) catalysts (also referred to as polyvalent aryloxyether catalysts).
  • LLDPE includes linear, substantially linear, or heterogeneous ethylene-based copolymers. LLDPEs contain less long chain branching than LDPEs and include the substantially linear ethylene polymers, which are further defined in U.S.
  • a loop reactor 100 may comprise a continuous pipe that runs in a loop 102. Ethylene and copolymer may polymerize via a solution phase polymerization process, in the presence of a catalyst, within the loop 102 of continuous pipe.
  • the loop 102 may comprise a first half 104, and a second half 110.
  • the first half 104 is the space between an outlet 106b of a second heat exchanger 106 and an outlet 108b of first heat exchanger 108; and the second half 110 is the space between an outlet 108b of the first heat exchanger 108 and an outlet 106b of the second heat exchanger 106.
  • Catalyst may be introduced to the loop reactor 100 via a first catalyst injection point 112.
  • Ethylene and comonomer may be introduced to the loop reactor 100 via a first feed injection point 114.
  • ethylene and comonomer may be introduced through a single injection point. In alternate embodiments, ethylene and comonomer may be introduced through separate injection points.
  • ethylene and comonomer may be introduced within the first half 104 at the first feed injection point 114.
  • each of ethylene, comonomer, and catalyst may be introduced to the first half 104 by more than one injection point (e.g., there may be 1, 2, 3, or 4 ethylene injection points in the first half 104; 1, 2, 3, or 4 comonomer injection points in the first half 104; and/or 1, 2, 3, or 4 catalyst injection points in the first half 104).
  • the location of the first feed injection point 114 and the first catalyst injection point 112 within the first half 104 is not particularly limited, such that the first feed injection point 114 and the first catalyst injection point 112 need not be located adjacent to a heat exchanger.
  • a single, combined injector may be utilized to introduce the ethylene, comonomer, and catalyst to the first half 104.
  • the first feed injection point 114 may also be the first catalyst injection point 112.
  • the catalyst, ethylene, and comonomer may polymerize, within loop 102, to form an ethylene-based polymer and release heat. Still within loop 102, the catalyst, ethylene, comonomer, and ethylene may pass to a first heat exchanger 108.
  • first heat exchanger 108 heat may be transferred from the loop 102 to first heat exchanger cold feed 116, thereby forming first heat exchanger hot effluent 118.
  • the catalyst, ethylene, and comonomer may then pass to second half 110, which begins at the outlet 108b of the first heat exchanger 108.
  • additional catalyst may be introduced to loop 102 via a second catalyst injection point 120.
  • Additional ethylene and comonomer may be introduced to loop 102 via a second feed injection point 122.
  • ethylene and comonomer may be introduced through a single injection point. In alternate embodiments, ethylene and comonomer may be introduced through separate injection points.
  • the ethylene and comonomer may be introduced within the second half 110 at the second feed injection point 122.
  • each of ethylene, comonomer, and catalyst may be introduced to the second half 110 by more than one injection point (e.g., there may be 1, 2, 3, or 4 ethylene injection points in the second half 110; 1, 2, 3, or 4 comonomer injection points in the second half 110; and/or 1, 2, 3, or 4 catalyst injection points in the second half 110).
  • the location of the second feed injection point 122 and the second catalyst injection point 120 within the second half 110 is not particularly limited, such that the second feed injection point 122 and the second catalyst injection point 120 need not be located adjacent to a heat exchanger.
  • a single, combined injector may be utilized to introduce the ethylene, comonomer, and catalyst to the second half 110.
  • the second feed injection point 122 may also be the second catalyst injection point 120.
  • the number of feed injection points may equal the number of catalyst injection points.
  • the loop reactor 100 may include two feed injection points and two catalyst injection points, three feed injection points and three catalyst injection 85922-WO-PCT/DOW 85922 WO points, four feed injection points and four catalyst injection points, or even five feed injection points and five catalyst injection points.
  • the number of ethylene injection points may equal the number of catalyst injection points.
  • the loop reactor 100 may include two ethylene injection points and two catalyst injection points, three ethylene injection points and three catalyst injection points, four ethylene injection points and four catalyst injection points, or even ethylene feed injection points and five catalyst injection points.
  • the produced ethylene-based polymer may be removed from loop reactor 100 via reactor outlet 124.
  • Processes for Producing Ethylene-Based Polymers are directed to a process for forming an ethylene-based polymer. Still referring to FIG. 1, the process may comprise introducing catalyst to a loop reactor 100 through at least two catalyst injection points 112, 120.
  • the loop reactor 100 may comprise a first half 104 and a second half 110.
  • the first catalyst injection point 112 may be positioned in the first half 104 and the second catalyst injection point 120 may be positioned in the second half 110.
  • the process may further comprise introducing ethylene and a comonomer to the loop reactor 100 through at least two feed injection points 114, 122.
  • the first feed injection point 114 may be positioned in the first half 104 of the loop 102 and the second feed injection point 122 may be positioned in the second half 110 of the loop 102.
  • the comonomer may comprise olefins, such as C 3 -C 14 olefins, such as C 3 -C 14 ⁇ - olefins.
  • Contemplated comonomers include, by way of example but not limitation, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1- dodecene, 1-tridecene, and 1-tetradecene.
  • the catalyst may comprise conventional solution polyethylene polymerization catalysts.
  • the catalyst may comprise Ziegler-Natta catalysts, metallocene catalysts, and post-metallocene catalysts.
  • the process may comprise polymerizing the ethylene and comonomer to form the ethylene-based polymer.
  • the process may comprise polymerizing the ethylene and comonomer while controlling one or more polymerization conditions (e.g., a ratio of catalyst injected at the second catalyst injection point 120 to catalyst injected at the first catalyst injection point 112) such that a ratio of an amount of polymerization in the first half 104 to an amount of polymerization in the second half 110 is from 0.7 to 1.3, such as from 0.8 to 1.2, from 0.9 to 1.1, from 0.95 to 1.05, from 0.7 to 0.8, from 0.8 to 0.9, from 0.9 to 1.0, from 1.0 to 1.1, from 1.1 to 1.2, from 1.2 to 1.3, or any combination of two or more of these ranges.
  • the process may comprise controlling one or more polymerization conditions (e.g., a ratio of catalyst injected at the second catalyst injection point 120 to catalyst injected at the first catalyst injection point 112) such that a ratio of the heat of polymerization in the first half 104 to the heat of polymerization in the second half 110 is from 0.7 to 1.3.
  • the ratio of the amount and/or heat of polymerization in the first half 104 to the amount and/or heat of polymerization in the second half 110 may be controlled by controlling the amount of catalyst fed to each of the first half 104 and the second half 110.
  • the ratio of catalyst injected at the second catalyst injection point 120 to the catalyst injected at the first catalyst injection point 112 is from 0.7 to 1.3, such as from 0.8 to 1.2, from 0.9 to 1.1, from 0.95 to 1.05, from 0.7 to 0.8, from 0.8 to 0.9, from 0.9 to 1.0, 85922-WO-PCT/DOW 85922 WO from 1.0 to 1.1, from 1.1 to 1.2, from 1.2 to 1.3, or any combination of two or more of these ranges.
  • the process may comprise measuring the heat of polymerization in the first half 104 and the heat of polymerization in the second half 110.
  • the process may then comprise controlling the amount of catalyst to the first catalyst injection point 112 and the second catalyst injection point 120, based on the ratio of heat generated in the first half 104 and the heat generated in the second half 110.
  • the process may comprise increasing the proportion of catalyst to the second catalyst injection point 120, if the ratio of the heat of polymerization in the first half 104 to the heat of polymerization in the second half 110 is greater than 1.2.
  • the process may comprise decreasing the proportion of catalyst to the second catalyst injection point 120, if the ratio of the heat of polymerization in the first half 104 to the heat of polymerization in the second half 110 is less than 0.8.
  • Catalyst half-life refers to the time it takes for 50% of the catalyst in the reactor to be deactivated. Without being limited by theory, when only one catalyst injector is used in the loop reactor 100, more material is made in the first half 104 (nearest the catalyst injection) and less material in the second half 110 as a result of catalyst deactivation.
  • a half-life of the catalyst in the loop reactor 100 is less than 80% of a recirculation time of the catalyst in the loop reactor 100, such as less than 70%, less than 60%, or less than 50%. Generally, when catalyst half- lives relative to recirculation times are shorter, the importance of multiple injection points increases.
  • polymerizing the ethylene and comonomer may occur at a temperature of from 180 oC to 210 oC, such as from 180 oC to 185 oC, from 185 oC to 190 oC, from 190 oC to 195 oC, from 195 oC to 200 oC, from 200 oC to 205 oC, from 205 oC to 210 oC, or any combination of two or more of these ranges.
  • 85922-WO-PCT/DOW 85922 WO polymerizing at too low of a temperature, such as below 180 oC results in lower production rates and undesirably increased polymer solution viscosity.
  • the loop reactor 100 may comprise a first heat exchanger 108 and a second heat exchanger 106.
  • the first catalyst injection point 112 and first feed injection point 114 may be upstream of the first heat exchanger 108 and downstream of the second heat exchanger 106.
  • the second catalyst injection point 120 and the second feed injection point 122 may be upstream of the second heat exchanger 106 and downstream of the first heat exchanger 108.
  • processes may comprise controlling the ratio of catalyst injected at the first catalyst injection point 112 to the catalyst injected at the second catalyst injection point 120 such that a ratio of heat extracted at the second heat exchanger to heat extracted at the first heat exchanger may be from 0.7 to 1.3, such as from 0.8 to 1.2, from 0.9 to 1.1, from 0.95 to 1.05, from 0.7 to 0.8, from 0.8 to 0.9, from 0.9 to 1.0, from 1.0 to 1.1, from 1.1 to 1.2, from 1.2 to 1.3, or any combination of two or more of these ranges.
  • controlling the ratio of catalyst injected at the first catalyst injection point 112 to the catalyst injected at the second catalyst injection point 120 based upon the ratio of heat extracted at the two heat exchanges may enable easy and cost effective monitoring of the reaction, without the need for additional monitoring equipment or simulations.
  • the ratio of catalyst injected at the second catalyst injection point 120 to the catalyst injected at the first catalyst injection point 112 may be a mass flow ratio or a volumetric flow ratio.
  • the catalyst injected at the second catalyst injection point 120 may be the same as the catalyst injected at the first catalyst injection point 112.
  • Ethylene-Based Polymers In embodiments, less than 8 wt.
  • % of the polymer has a high temperature thermal gradient interaction chromatography (also referred to as “HT-TGIC” or “TGIC”) elution 85922-WO-PCT/DOW 85922 WO temperature less than 80 °C.
  • HT-TGIC high temperature thermal gradient interaction chromatography
  • elution 85922-WO-PCT/DOW 85922 WO temperature less than 80 °C.
  • less than 7 wt. %, less than 6.5 wt. %, less than 6.0 wt. %, less than 5.5 wt. %, less than 5.3 wt. %, less than 5.0 wt. %, less than 4.8 wt. %, less than 4.6 wt. %, or even less than 4.3 wt. % of the polymer may have a TGIC elution temperature less than 80 °C.
  • the ethylene-based polymer has a density of from 0.85 to 0.94 g/cc, such as from 0.85 to 0.87 g/cc, from 0.87 to 0.89 g/cc, from 0.89 to 0.91 g/cc, from 0.91 to 0.93 g/cc, from 0.93 to 0.94 g/cc, or any combination of two or more of these ranges.
  • the ethylene-based polymer has a melt index (I 2 ) of from 0.2 to 2000 dg/min, such as from 0.2 to 0.5 dg/min, from 0.5 to 5 dg/min, from 5 to 20 dg/min, from 20 to 50 dg/min, from 50 to 200 dg/min, from 200 to 500 dg/min, from 500 to 1000 dg/min, from 1000 to 2000 dg/min, or any combination of two or more of these ranges.
  • TEST METHODS TGIC High temperature thermal gradient interaction chromatography (HT-TGIC) was determined according to the methods disclosed in U.S. Pat. No.
  • the TGIC chromatogram is related to comonomer content and its distribution. The distribution gets broader with the increase in comonomer content according to Stockmeyer equation. It can also be related to the number of catalyst active sites (Soares et al., Polyolefin reaction engineering Wiley-VCH, Polyolefin Microstructural modeling, Chapter 6) or the process conditions. (For general knowledge, please refer to Stregel, et al., “Modern size- exclusion liquid chromatography, Wiley, 2 nd edition, Chapter 3).
  • the broadness of the chemical composition distribution can be quantified by the ratio of broadness of TGIC profile at different maximum heights, for example, the ratio of the broadness of TGIC profile at 1/4 maximum height to the broadness of TGIC profile at 1/4 maximum. 85922-WO-PCT/DOW 85922 WO [0047]
  • the procedure of TGIC profile width is the following: 1. Run samples and the Eicosane/iPP/homopolymer polyethylene mixture in the same run queue according to the TGIC method above. If not in same run queue, samples may be run over a very short time period in the same TGIC instrument (to minimize variability in IR detector response and broadness).
  • the peak width at 1/4 of HDPE in the Eicosane/iPP/homopolymer polyethylene mixture must be ⁇ 1%RSD to be able to compare TGIC profile width of the samples of interest; 2. Generate TGIC chromatograms dWi/dT versus elution temperature (T); 3. For each sample, obtain the maximum height from the TGIC chromatogram (dWi/dTi) by searching each data point for the highest intensity from 35.0 o C to 170.0 o C, the corresponding elution temperature of TGIC chromatogram at the maximum height is defined as profile temperature (Tp).
  • the profile width (1/4) is defined as the temperature difference between the front temperature and the rear temperature at 1/4 of the maximum height, the front temperature at the 1/4 of the maximum height is searched forward from 35.0 o C, while the rear temperature at the 1/4 of the maximum height is searched backward from 170.0 o C. 4.
  • the peak elution temperature of homopolymer polyethylene HDPE is set at 150 °C. 5.
  • Broadness of TGIC profile at 1/4 th maximum height is defined as: Density [0048] Samples for density measurement are prepared according to ASTM D 1928.
  • the levels of these four species were varied to produce a final polymer at a rate of 450 lb/hr, a melt index of 1.0 dg/min, and a density of 0.870 g/cc at a reactor polymer concentration of 29%.
  • Catalyst and cocatalyst were added to convert 91% of the ethylene added to the reactor.
  • Catalyst was added at either a single injection point or split between a first catalyst injection point in the first half of the reactor and at a catalyst injection point in the second half of the reactor.
  • the temperature of the reactor was controlled by adjusting the temperature of the cooling water utilized in the two exchangers.
  • the recirculation time in the reactor loop for all these experiments was 98 seconds.
  • Catalyst A is a bis-biphenyl phenoxy catalyst, depicted as Formula I below.
  • Catalyst A was activated with 1.2 equivalents of the cocatalyst (Amines, bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-)) (CAS# 200644-82-2).
  • 85922-WO-PCT/DOW 85922 WO Table 1 [0053] The TGIC spectra of C-1 and E-1 are provided in FIG. 3.
  • TGIC spectra of C-2 and E-2 are provided in FIG. 4. As can be seen from Table 1, FIG. 3, and FIG.
  • Catalyst B is a bis-biphenyl phenoxy catalyst, depicted as Formula II below.
  • Catalyst B was activated with 1.2 equivalents of the cocatalyst (Amines, bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl) borate(1-)) (CAS# 200644-82-2).Process conditions are given in Table 2. 85922-WO-PCT/DOW 85922 WO Table 2 [0055] The TGIC spectra of C-3 and E-3 are provided in FIG. 5. As can be seen from FIG. 5 and Table 2, the addition of a second catalyst injector narrows the polymer short chain branching distribution, as indicated in a decrease of both the polymer broadening and the fraction of material with a TGIC temperature ⁇ 80 ⁇ C. As catalyst B has a relatively short half- life, the effect of a second catalyst injector is relatively pronounced.
  • the cocatalyst Amines, bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)

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

Abstract

Selon certains modes de réalisation de la présente invention, un procédé de formation d'un polymère à base d'éthylène peut comprendre : l'introduction d'un catalyseur dans un réacteur à boucle à travers au moins deux points d'injection de catalyseur, où la boucle comprend une première moitié et une seconde moitié, et le premier point d'injection de catalyseur est dans la première moitié de la boucle et le second point d'injection de catalyseur est dans la seconde moitié de la boucle ; et la polymérisation de l'éthylène et du copolymère tout en contrôlant une ou plusieurs conditions de polymérisation de telle sorte que : un rapport d'une quantité de polymérisation dans la première moitié à une quantité de polymérisation dans la seconde moitié est de 0,7 à 1,3 ; un rapport de la chaleur de polymérisation dans la première moitié à la chaleur de polymérisation dans la seconde moitié est de 0,7 à 1,3 ; ou les deux, formant ainsi le polymère à base d'éthylène.
PCT/US2025/023154 2024-04-08 2025-04-04 Procédé de production de polyéthylènes Pending WO2025216983A1 (fr)

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