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WO2025177030A1 - Système de réacteur de polymérisation et procédé de production d'une composition de polyéthylène multimodal, composition de polyéthylène multimodal obtenue à partir de celui-ci et tuyau comprenant ladite composition - Google Patents

Système de réacteur de polymérisation et procédé de production d'une composition de polyéthylène multimodal, composition de polyéthylène multimodal obtenue à partir de celui-ci et tuyau comprenant ladite composition

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Publication number
WO2025177030A1
WO2025177030A1 PCT/IB2024/051793 IB2024051793W WO2025177030A1 WO 2025177030 A1 WO2025177030 A1 WO 2025177030A1 IB 2024051793 W IB2024051793 W IB 2024051793W WO 2025177030 A1 WO2025177030 A1 WO 2025177030A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydrogen
ranging
reaction stream
molecular weight
polyethylene composition
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
PCT/IB2024/051793
Other languages
English (en)
Inventor
Patcharaporn CHUAYPLOD
Sanchai THONGKHAM
Danai KITKANNIKA
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.)
IRPC PCL
Original Assignee
IRPC PCL
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 IRPC PCL filed Critical IRPC PCL
Priority to PCT/IB2024/051793 priority Critical patent/WO2025177030A1/fr
Publication of WO2025177030A1 publication Critical patent/WO2025177030A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • 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
    • 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
    • C08F6/00—Post-polymerisation treatments
    • C08F6/001—Removal of residual monomers by physical means
    • C08F6/005—Removal of residual monomers by physical means from solid polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the present invention relates to a polymerization reactor system and a process for producing a multimodal polyethylene composition, a multimodal polyethylene composition obtained therefrom and a pipe comprising the said composition.
  • Multimodal polyolefin resins are widely used in industrial applications due to their combined advantages: enhanced processability from a lower molecular weight fraction and superior physical properties attributed to a higher molecular weight component.
  • One of the traditional ways to create these multimodal resins often involves blending different resins with varying molecular weight distributions, however, this method is troubled by extra processing steps and the challenge of achieving a uniform product. Such blends not only add to production costs but also tend to yield resins with inferior properties compared to those produced via in situ methods.
  • a more efficient approach involves preparing a multimodal polyethylene via a multistage reaction sequence comprising successive polymerization steps carried out under predetermined different reaction conditions in respective reactors arranged in series so as to obtain polyethylene fractions with different molecular weights.
  • a process of this type can be performed in conditions where monomers and a molar mass regulator, preferably hydrogen, are firstly polymerized in a first reactor under initial reaction conditions in the presence of a suspension medium and a suitable catalyst. The resulting product is then transferred to a second reactor for further polymerization under different reaction conditions. If, for instance, trimodal polyethylene is the desired outcome, it can be further transferred to a third reactor and polymerized under third reaction conditions, distinct from the first and second conditions, to obtain three polyethylene fractions with different molecular weights.
  • a molar mass regulator preferably hydrogen
  • US 6,716,936 B 1 discloses the utilization of two or more light solvent boiling pool reactors in series, enabling the polymerization of ethylene and comonomers to yield bimodal polyethylene copolymers.
  • the process involves introducing catalyst solely into the first reactor, operating it at high hydrogen compositions, and utilizing a series of connected flash drums to eliminate hydrogen from the polymer slurry product stream of the first reactor. This method facilitates the production of homogeneous, high molecular weight bimodal polyethylene resins.
  • US 2003/0191251 Al discloses a polyethylene production process utilizing a series of slurry reactors, incorporating an intermediate slurry transfer reactor and a hydrogen removal apparatus.
  • the production of a multimodal polymer occurs within interconnected reactors.
  • the first reactor employs a light solvent as the slurry medium and hydrogen to regulate polymer molecular weight.
  • the polymer output from the first reactor undergoes thorough hydrogen removal before entering a subsequent polymerization reactor. This subsequent reactor operates at low hydrogen pressure to produce a high molecular weight olefin.
  • WO 2007/022908 A2 discloses a polyethylene molding composition having a multimodal molecular mass distribution which is suitable for producing pipes having excellent mechanical properties.
  • the PE molding composition is prepared in a cascaded suspension polymerization process which is carried out with the highest hydrogen concentration being set in the first reactor. In the subsequent, further reactors, the hydrogen concentration is gradually reduced, so that the hydrogen concentration used in the third reactor is lower with respect to hydrogen concentration used in the second reactor.
  • the present invention is developed to address the aforementioned need, and in the first aspect, it aims to provide a polymerization reactor system.
  • This reactor system is adapted for producing a multimodal polyethylene composition by improving reactor configuration, optimizing polymerization conditions within each reactor, and controlling hydrogen removal content at each stage. These improvements aim to produce a multimodal polyethylene composition that meets specified criteria.
  • Another objective of the present invention is to introduce a process for producing a multimodal polyethylene composition, utilizing the aforementioned reactor system. This process is developed to yield the multimodal polyethylene composition with desired properties.
  • Yet another objective of the present invention is to provide a multimodal polyethylene composition obtained from the system and process of the present invention, featuring improved properties.
  • this polyethylene composition exhibits characteristics suitable for pipe, blow molded, and extrusion molding applications. More specifically, it possesses attributes necessary to meet the specifications of PE100 pipes.
  • the present invention relates to a polymerization reactor system for producing a multimodal polyethylene composition.
  • the reactor system comprises: a first parallel reactor configured to polymerize ethylene and produce a first reaction stream comprising a low molecular weight polyethylene homopolymer with a weight average molecular weight (Mw) ranging from 25,000-55,000 g/mol, as determined by gel permeation chromatography (GPC); a first degassing unit, in communication with the first parallel reactor, configured to remove hydrogen from the first reaction stream, resulting in a hydrogen-depleted first reaction stream; a second parallel reactor configured to polymerize ethylene and produce a second reaction stream comprising a first high molecular weight polyethylene homopolymer or copolymer with a weight average molecular weight ranging from 100,000-650,000 g/mol, as determined by GPC; a second degassing unit, in communication with the second parallel reactor, configured to remove hydrogen from the second reaction stream, resulting in a hydrogen-depleted second reaction stream; and
  • the first and second parallel reactors are configured to operate concurrently in parallel, while the serial reactor is configured to operate sequentially after the first and second parallel reactors.
  • the first degassing unit is configured to remove at least 97% by weight of hydrogen from the total hydrogen content within the first reaction stream
  • the second degassing unit is configured to remove at least 99% by weight of hydrogen from the total hydrogen content within the second reaction stream.
  • the present invention relates to a process for producing a multimodal polyethylene composition which utilizes the polymerization reactor system of the first aspect.
  • the process comprises the steps of:
  • the steps (i) and (iii) operate concurrently in parallel, while the step (v) operates sequentially after the steps (ii) and (iv). More preferably, the step (ii) operates to remove at least 97% by weight of hydrogen from the total hydrogen content within the first reaction stream, and the step (iv) operates to remove at least 99% by weight of hydrogen from the total hydrogen content within the second reaction stream.
  • the third aspect of this invention relates to a multimodal polyethylene composition obtained from the process according to the present invention.
  • the multimodal polyethylene composition of the present invention comprises:
  • the last aspect of the present invention pertains to a pipe comprising the multimodal polyethylene composition as described in the third aspect of the invention.
  • this pipe is a PElOO-qualified pipe designed for applications under a pressure of at least 10.0 MPa.
  • the reactor configuration and operational conditions within the present invention's reactor system and process result in polyethylene powder products exhibiting desirable properties. These properties are particularly crucial for meeting the specifications of pipe materials with a designation code PE100, encompassing attributes like Notch Charpy impact resistance tested in accordance with ISO 790, strain hardening capabilities, and suitability for hydrostatic pressure applications.
  • Fig. 1 illustrates a simplified diagram of the polymerization reactor system for producing a multimodal polyethylene composition according to the present invention.
  • consist( s) of’ and its variation such as “ consisting of’ and “ consisted of’ , “ comprise( s) ” and its variation such as “comprising” and “comprised” , “ has/ have/ having” , “contain(s)”, “ include( s) ” and its variation such as “ including” and “ included” are open- ended verbs.
  • any methods that “consist of’, “comprise”, “have” or “include” one or more components or steps are not limited only to the one or more components or steps, but also cover the components or steps that are not mentioned.
  • multimodal polyethylene composition or “multimodal polyethylene” used in the present invention refer to a polyethylene composition or polyethylene characterized by a molecular mass distribution curve displaying multimodal features. This indicates the presence of numerous ethylene polymer fractions, each possessing individual and discernible molecular weights.
  • polyethylene homopolymer refers to a polymer primarily composed of repeating units derived from ethylene. These homopolymers typically contain a high percentage of such units, with compositions ranging from at least 99% to 100% by weight originating from ethylene.
  • polyethylene copolymer refers to a polymer incorporating repeating units sourced from both ethylene and a minimum of one other monomer. Typically, polyethylene copolymers will not comprise more than 15 % by weight of repeat units deriving from monomers other than ethylene.
  • hydrox-depleted reaction stream used in the present invention refers to a stream resulting from a reaction that contains less hydrogen than the initial amount supplied to the reactors during the polymerization process.
  • the "hydrogen-depleted first reaction stream” refers to the stream processed by the first degassing unit, containing no more than 3% by weight of hydrogen from the initial hydrogen content within that particular reaction stream.
  • the “hydrogen-depleted second reaction stream” refers to the stream processed by the second degassing unit, holding no more than 1 % by weight of hydrogen from the total hydrogen content within that second reaction stream.
  • the second reaction stream devoid of hydrogen is preferred.
  • a low molecular weight polyethylene refers to a polymer with a molecular weight lower than that of a high molecular weight polyethylene.
  • molecular weight when used, refers to the weight average molecular weight unless explicitly stated otherwise.
  • the first aspect of the present invention involves a polymerization reactor system designed for producing a multimodal polyethylene composition.
  • This system comprises three distinct reactors connected in a mixed mode: the first and second parallel reactors run concurrently, operating in parallel, while the third reactor operates sequentially after the first and second parallel reactors.
  • Each reactor is set with different reaction conditions.
  • Fig. 1 provides a simplified diagram illustrating an embodiment of the polymerization reactor system according to the present invention.
  • This reactor system includes a first parallel reactor (RIA) and a second parallel reactor (RIB) configured to operate simultaneously in parallel.
  • the first parallel reactor (RIA) is designed to polymerize ethylene, generating a first reaction stream that consists of a low molecular weight polyethylene homopolymer.
  • This homopolymer possesses a weight average molecular weight (Mw) ranging from 25,000-55,000 g/mol, as determined via gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the second parallel reactor (RIB) polymerizes ethylene to produce a second reaction stream containing a high molecular weight polyethylene homopolymer or copolymer.
  • the reactor system comprises a serial reactor (R2) operating after the first and second parallel reactors (RIA and RIB).
  • This serial reactor (R2) polymerizes ethylene, along with the hydrogen-depleted first and second reaction streams, to produce a third reaction stream.
  • This third reaction stream contains a high molecular weight polyethylene copolymer characterized by a weight average molecular weight ranging from 150,000-380,000 g/mol, determined via GPC.
  • the first degassing unit (DI) it is preferable for the first degassing unit (DI) to remove at least 97% by weight of hydrogen from the total hydrogen content within the first reaction stream.
  • the second degassing unit (D2) should remove at least 99% by weight of hydrogen from the total hydrogen content within the second reaction stream. This level of hydrogen removal has been demonstrated to yield the desired properties in the multimodal polyethylene composition.
  • the present reactor system may further incorporate a flash vessel (F), in communication with the first and second degassing units (DI and D2).
  • the first and second degassing units (DI and D2) in conjunction with the flash vessel (F) will employ a pressure balance mechanism to facilitate hydrogen removal process.
  • the polymerization conditions in each reactor are optimized to achieve the desired polyethylene product.
  • the first parallel reactor (RIA) operates at a temperature ranging from 80-85°C and a pressure ranging from 8-9 bar.
  • the second parallel reactor (RIB) operates at a temperature ranging from 70-80°C and a pressure ranging from 1.5-3 bar.
  • the serial reactor (R2) operates at a temperature ranging from 70-75°C and a pressure ranging from 1.5-3 bar.
  • the first degassing unit (DI) operates at a temperature ranging from 60-70°C and a pressure ranging from 1.2- 1.6 bar.
  • the second degassing unit (D2) operates at a temperature ranging from 65-80°C and a pressure ranging from 1.2- 1.6 bar.
  • the flash vessel operates at a pressure equal to or less than 1.3 bar.
  • the second aspect of the present invention relates to a process for producing a multimodal polyethylene composition.
  • the process involves employing the previously described polymerization reactor system and comprises the following steps:
  • the steps (i) and (iii) operate concurrently in parallel, while the step (v) operates sequentially after the steps (ii) and (iv).
  • the step (ii) operates to remove at least 97% by weight of hydrogen from the total hydrogen content within the first reaction stream, and the step (iv) operates to remove at least 99% by weight of hydrogen from the total hydrogen content within the second reaction stream.
  • the steps (ii) and (iv) operate in conjunction with a flash vessel to employ a pressure balance mechanism to remove hydrogen.
  • the step (i) operates at a temperature ranging from 80-85°C and a pressure ranging from 8-9 bar.
  • the step (iii) operates at a temperature ranging from 70-80°C and a pressure ranging from 1.5-3 bar.
  • the step (v) operates at a temperature ranging from 70-75°C and a pressure ranging from 1.5-3 bar.
  • the comonomer is preferably a C4 to Cl 2 a-olefin comonomer.
  • the comonomer is n-butene or n-pentene and most preferably it is n-butene, such as 1 -butene.
  • the hydrocarbon medium is preferably a hydrocarbon of 3-10 carbon atoms.
  • One example used in this invention is hexane.
  • hydrogen is introduced into the process at step (i) and optionally at step (iii) to act as a regulator for molecular weight. Subsequently, this hydrogen undergoes removal in two stages, with specific quantities removed at each stage. The initial removal of hydrogen occurs within the first degassing unit (DI), achieving a removal rate of at least 97% by weight. The subsequent removal takes place in the second degassing unit (D2), targeting a removal rate of at least 99% by weight, in comparison to the total hydrogen content within the reaction stream from the first and second parallel reactors (RIA and RIB), respectively. It's crucial to emphasize that this reactor configuration and the specified hydrogen removal rates differ significantly from conventional methods and haven't been disclosed in prior literature.
  • the low molecular weight polyethylene homopolymer has a density ranging from 0.967-0.972 g/cm 3 .
  • the first high molecular weight polyethylene homopolymer or copolymer has a density ranging from 0.930-0.950 g/cm 3 .
  • the second high molecular weight polyethylene copolymer has a density ranging from 0.945-0.962 g/cm 3 . More preferably, the second high molecular weight polyethylene copolymer has the density ranging from 0.945-0.954 g/cm 3 . All specified densities were measured in accordance with ISO 1183.
  • the multimodal polyethylene composition of the present invention exhibits enhanced mechanical and physical properties.
  • this composition has a crystallinity ranging from 63-78%, more preferably, ranging from 63-73%.
  • the composition has a molecular weight distribution (Mw/Mn) ranging from 27-39, as determined by GPC, and a strain hardening modulus (Gp) of at least 21.5 MPa.
  • the multimodal polyethylene composition of this invention may be compounded with additional additives to yield a polyethylene resin with improved mechanical and physical properties.
  • additional additives can be any substance recognized within the polymer field, such as heat stabilizers, antioxidants, UV absorbers, light stabilizers, fillers, reinforcing materials, plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flame retardants, antistatics, blowing agents, or their combinations.
  • the quantity of these additional additives can be adjusted to align with the desired properties of the resin product.
  • the amount of additional additives can range from 0-50% by weight, preferably 0-10% by weight range based on the total weight of the resin mixture.
  • the obtained polyethylene resin may then be molded or extruded to a desired product.
  • the polyethylene composition according to this invention, as well as the polyethylene resin comprising this composition proves particularly well-suited for the production of pipes, blow molding, and extrusion molding applications.
  • This multimodal polyethylene composition and the resulting polymer resin exhibit enhanced mechanical properties, including Notch Charpy impact resistance tested in accordance with ISO 790, robust strain hardening capabilities, and suitability for hydrostatic pressure applications. These properties are especially crucial for manufacturing end products that demand high-pressure resistance, such as a PElOO-qualified pipe utilized in applications operating under pressures of at least 10.0 MPa.
  • the polymerization in the first parallel reactor (RIA) was carried out to produce a first reaction stream, subsequently transferred to the first degassing unit (DI).
  • the polymerization in the second parallel reactor (RIB) was carried out to produce a second reaction stream, which was then directed to the second degassing unit (D2).
  • first degassing unit (DI) hydrogen was partially removed from the first reaction stream, resulting in a hydrogen-depleted first reaction stream subsequently transferred to the serial reactor (R2).
  • the second degassing unit (D2) all or almost all hydrogen was removed from the second reaction stream, resulting in a hydrogen-depleted second reaction stream also transferred to the serial reactor (R2).
  • Remark (1) “EE ratio RIA” refers to the content in wt% of the low molecular weight polyethylene homopolymer obtained from the first parallel reactor (RIA), based on the total weight of the multimodal polyethylene composition.
  • Remark (2) “EE ratio RIB” refers to the content in wt% of the first high molecular weight polyethylene homopolymer/copolymer obtained from the second parallel reactor (RIB), based on the total weight of the multimodal polyethylene composition.
  • E ratio R2 refers to the content in wt% of the second high molecular weight polyethylene copolymer obtained from the serial reactor (R2), based on the total weight of the multimodal polyethylene composition.
  • Strain hardening modulus was measured according to ISO 18488.
  • the polymerization reactor system and process of the present invention yield a multimodal polyethylene composition s featuring enhanced properties, particularly those crucial for manufacturing pipes, blow-molded, and extrusion-molded products.
  • the resin pellets containing this invention's composition demonstrate commendable traits, notably a high strain hardening capacity - each example presenting a strain hardening value surpassing 30 MPa.
  • these resin pellets, incorporating the composition of this invention successfully meet the criteria for the hydrostatic test at 20°C.

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

Abstract

La présente invention concerne un système de réacteur de polymérisation et un procédé de production d'une composition de polyéthylène multimodal. Le système de réacteur de polymérisation comprend un premier réacteur parallèle et une première unité de dégazage associée, un second réacteur parallèle et une seconde unité de dégazage associée, et un réacteur en série. Les premier et second réacteurs parallèles fonctionnent simultanément, tandis que le réacteur en série fonctionne séquentiellement après les premier et second réacteurs parallèles. Le procédé de la présente invention utilise le système de réacteur mentionné et comprend les étapes consistant à polymériser de l'éthylène dans le premier réacteur parallèle et à subir une élimination d'hydrogène ; à polymériser de l'éthylène dans le second réacteur parallèle et à subir une élimination d'hydrogène ; puis à polymériser de l'éthylène, le premier flux de réaction appauvri en hydrogène et le second flux de réaction appauvri en hydrogène dans le réacteur en série. De plus, l'invention concerne une composition de polyéthylène multimodal obtenue à partir de ce procédé, et un tuyau comprenant cette composition.
PCT/IB2024/051793 2024-02-25 2024-02-25 Système de réacteur de polymérisation et procédé de production d'une composition de polyéthylène multimodal, composition de polyéthylène multimodal obtenue à partir de celui-ci et tuyau comprenant ladite composition Pending WO2025177030A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/IB2024/051793 WO2025177030A1 (fr) 2024-02-25 2024-02-25 Système de réacteur de polymérisation et procédé de production d'une composition de polyéthylène multimodal, composition de polyéthylène multimodal obtenue à partir de celui-ci et tuyau comprenant ladite composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IB2024/051793 WO2025177030A1 (fr) 2024-02-25 2024-02-25 Système de réacteur de polymérisation et procédé de production d'une composition de polyéthylène multimodal, composition de polyéthylène multimodal obtenue à partir de celui-ci et tuyau comprenant ladite composition

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WO2025177030A1 true WO2025177030A1 (fr) 2025-08-28

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013113797A1 (fr) * 2012-01-31 2013-08-08 Norner As Polymères polyéthylène multimodaux et procédé de préparation desdits polymères
US20190359741A1 (en) * 2016-09-12 2019-11-28 Thai Polyethylene Co., Ltd. Multimodal polyethylene pipe
US20230192913A1 (en) * 2016-09-12 2023-06-22 Thai Polyethylene Co., Ltd. Reactor system for multimodal polyethylene polymerization

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013113797A1 (fr) * 2012-01-31 2013-08-08 Norner As Polymères polyéthylène multimodaux et procédé de préparation desdits polymères
US20190359741A1 (en) * 2016-09-12 2019-11-28 Thai Polyethylene Co., Ltd. Multimodal polyethylene pipe
US20230192913A1 (en) * 2016-09-12 2023-06-22 Thai Polyethylene Co., Ltd. Reactor system for multimodal polyethylene polymerization

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