WO2020205337A1 - 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 Download PDF

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Publication number
WO2020205337A1
WO2020205337A1 PCT/US2020/024449 US2020024449W WO2020205337A1 WO 2020205337 A1 WO2020205337 A1 WO 2020205337A1 US 2020024449 W US2020024449 W US 2020024449W WO 2020205337 A1 WO2020205337 A1 WO 2020205337A1
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WIPO (PCT)
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.)
Ceased
Application number
PCT/US2020/024449
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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
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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.)
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Publication date
Application filed by ExxonMobil Chemical Patents Inc filed Critical ExxonMobil Chemical Patents Inc
Priority to SG11202110447SA priority Critical patent/SG11202110447SA/en
Priority to CN202080026008.9A priority patent/CN113646074B/zh
Priority to EP20718116.5A priority patent/EP3946713A1/fr
Publication of WO2020205337A1 publication Critical patent/WO2020205337A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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

  • a“catalyst system” is the combination of at least one catalyst compound, at least one activator, and an optional co-activator.
  • 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.
  • 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.
  • 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 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 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.
  • 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).
  • 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.
  • 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,
  • 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.
  • 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.
  • 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.

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  • 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.
PCT/US2020/024449 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 Ceased WO2020205337A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
SG11202110447SA SG11202110447SA (en) 2019-04-05 2020-03-24 Controlling molecular weight distribution and chemical composition distribution of a polyolefin product
CN202080026008.9A CN113646074B (zh) 2019-04-05 2020-03-24 控制聚烯烃产物的分子量分布和化学组成分布
EP20718116.5A 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

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US201962829871P 2019-04-05 2019-04-05
US62/829,871 2019-04-05
EP19173841.8 2019-05-10
EP19173841 2019-05-10

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WO2020205337A1 true WO2020205337A1 (fr) 2020-10-08

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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112430282A (zh) * 2020-11-18 2021-03-02 浙江大学 一种低熔融指数的聚烯烃及其应用

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EP0495375A2 (fr) 1991-01-16 1992-07-22 The Dow Chemical Company Procédé de préparation de catalyseurs pour polymérisation par addition par oxydation de centres métalliques
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EP0516476A2 (fr) 1991-05-29 1992-12-02 Se-Kure Controls, Inc. Capteur antivol
EP0520732A1 (fr) 1991-06-24 1992-12-30 The Dow Chemical Company Catalyseur homogène de polymérisation d'olefines obtenu par élimination d'un ligand avec un acide de lewis
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EP0561476A1 (fr) 1992-03-18 1993-09-22 Akzo Nobel N.V. Solution de polyméthylaluminoxane avec stabilisation améliorée de la solution
US5235081A (en) 1992-03-18 1993-08-10 Ethyl Corporation Method of removing gel forming materials from methylaluminoxanes
EP0570982A1 (fr) 1992-05-22 1993-11-24 Tosoh Corporation Catalyseurs et procédé de préparation de polymères d'oléfine
US5502124A (en) 1992-07-01 1996-03-26 Exxon Chemical Patents Inc. Transition metal olefin polymerization processes
US5248801A (en) 1992-08-27 1993-09-28 Ethyl Corporation Preparation of methylaluminoxanes
WO1994010180A1 (fr) 1992-11-02 1994-05-11 Akzo N.V. Aryloxyaluminoxanes
WO1997036942A1 (fr) * 1996-04-01 1997-10-09 The Dow Chemical Company Polymerisation en solution d'olefines
WO2002038628A2 (fr) 2000-11-07 2002-05-16 Symyx Technologies, Inc. Ligands de pyridylamine substitues, complexes, catalyseurs et procedes pour la polymerisation, et polymeres
WO2003040201A1 (fr) 2001-11-06 2003-05-15 Dow Global Technologies Inc. Copolymeres de propylene isotactique, preparation et utilisation associees
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
WO2003040095A2 (fr) 2001-11-06 2003-05-15 Dow Global Technologies Inc. Cristallisation de polypropylene a l'aide d'un agent de nucleation semi-cristallin ramifie ou couple
WO2003040442A1 (fr) 2001-11-06 2003-05-15 Dow Global Technologies Inc. Fibres de copolymere de propylene isotactique, preparation et utilisation de ces dernieres
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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

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