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WO2009076152A1 - Mélange de copolymère à blocs polyéthylène-co-polypropylène syndiotactique et polyéthylène d'ultrahaute masse moléculaire - Google Patents

Mélange de copolymère à blocs polyéthylène-co-polypropylène syndiotactique et polyéthylène d'ultrahaute masse moléculaire Download PDF

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Publication number
WO2009076152A1
WO2009076152A1 PCT/US2008/085484 US2008085484W WO2009076152A1 WO 2009076152 A1 WO2009076152 A1 WO 2009076152A1 US 2008085484 W US2008085484 W US 2008085484W WO 2009076152 A1 WO2009076152 A1 WO 2009076152A1
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WIPO (PCT)
Prior art keywords
catalyst
polymer
catalyst system
polymerization
single site
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/US2008/085484
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English (en)
Inventor
Robert L. Jones, Jr.
Mahmoud Zohdi Armoush
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.)
DSM Biomedical Inc
Original Assignee
Polymer Technology Group Inc
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Filing date
Publication date
Application filed by Polymer Technology Group Inc filed Critical Polymer Technology Group Inc
Publication of WO2009076152A1 publication Critical patent/WO2009076152A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
    • C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
    • 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
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
    • C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
    • C08F297/083—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins the monomers being ethylene or propylene
    • 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
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/04—Dual catalyst, i.e. use of two different catalysts, where none of the catalysts is a metallocene

Definitions

  • the present invention relates to a method of preparing a material consisting of a mixture of a co-polymer and ultrahigh molecular weight polyethylene. More particularly, the present invention relates to a method of preparing a material consisting of a mixture of polyethylene- co-syndiotactic polypropylene block co-polymer and ultrahigh molecular weight polyethylene.
  • Pre-polymerization of supported polyolefm catalyst is an important method for improving the preparation and quality of material manufactured in commercial reactors.
  • pre- polymerization consists of treating activated catalyst with a small amount of olefin with the intention of coating or containing the catalyst matrix (in what has been described as a micro- reactor) prior to introducing the catalyst into the main process stream.
  • Catalyst treated in this fashion when challenged with downstream reactor conditions, becomes less susceptible to fragmentation (which can produce undesirable fine particles known to plug and/or clog downstream processing equipment) and produces more uniform particles having better average particle size and polymer bulk densities.
  • fouling due to agglomeration of the formed polymer particles is reduced, and operating conditions are generally improved.
  • pre-polymerization of catalyst used in polyolefm polymerization provides control over polymer particle morphology, less reactor fouling, and an improvement in post reactor processing of the material.
  • Pre-polymerization of ethylene catalysts with higher molecular weight olefins such as propylene (or a combination of olefins or di-olefins) provide a protective coating of polymer around the catalyst particle which later serves the purpose of modifying ethylene gas diffusion to the catalyst sites and/or rapid expansion of the catalyst particle providing control over the reaction process. In this manner, the morphology of the catalyst particle is better preserved during the polymerization reaction.
  • pre-polymerization conditions can vary for type and amount of material being produced, polyolefins may or may not be of the same or similar polymer types.
  • pre-polymerization using propylene for making ultrahigh molecular weight polyethylene (“UHMWPE”) polymer can be used as a method for controlling fouling and reactor-produced fines in commercial processes.
  • Propylene is used because of the reduced activity compared to ethylene, allowing the polymerization to proceed at a slower rate, coating the catalyst particle and protecting it from fragmentation.
  • a small coating of polypropylene (which is immiscible with polyethylene) encapsulates the catalyst particle and prevents catalyst particle fragmentation when it is introduced into the reactor system. Polypropylene residue remains as part of the pre-polymerization procedure using this monomer.
  • Loading an alternative catalyst onto the main catalyst support in addition to the catalyst intended for the bulk polymerization processes, could produce polymer(s) by encapsulating the catalyst particle and make a polymer having properties sufficiently different than the target polymer.
  • the pre-polymerization step could provide different structures and properties while still protecting the catalyst system.
  • a living single site catalyst system such as the phenoxy-imine (FI) catalyst loaded onto a classic Ziegler-Natta catalyst when pre-polymerized with propylene could produce a syndiotactic block, which would be followed with an ethylene block (due to the living nature of the catalyst system) when activation and polymerization with the Ziegler-Natta catalyst was carried out.
  • a polymer is prepared by first impregnating a living single site catalyst capable of synthesizing co-polymers into a silica-supported transition metal complex in order to create a catalyst system. Then, the catalyst system is activated and a pre-polymerization monomer mix is added. Next, the catalyst system and the pre-polymerization monomer is pre-polymerized until 0.1 to 25.0 grams of polymer per gram of catalyst is deposited on the catalyst surface to produce a pre-polymerized catalyst. Finally, the pre-polymerized catalyst is polymerized with olefinic monomer.
  • a phenoxy-imine catalyst has the disadvantage of producing weakly syndiotactic homo-polymers when polymerized in propylene.
  • the present invention relates to a catalyst system that takes advantage of the living character of a phenoxy-imine catalyst, making a polymer having a syndiotactic block and a miscible ethylene block.
  • the polymer made in this fashion, as part of the pre-polymerization catalyst coating process is also a compatibilizer.
  • the prepolymerization step when performed with a living catalyst will produce a polymeric coating formed from the initial monomers used for the pre-polymerization step and followed by the monomers used for the bulk polymerization. In essence, a block co-polymer chain is formed which is compatibilized with the bulk polymerization monomer.
  • the elements of added mass (amount of pre-polymer) formed and the molecular weight of the pre- polymerization step create a catalyst and polymer particle having better material properties (bulk density, processability), as well as fusion and material properties (reduced grain boundaries, interparticle tension, and co-monomer compatibility when the material is used in master batches as a compatibilizer).
  • Similar (although not living) catalysts which produce atactic high molecular weight polypropylene, could be added to a classic Ziegler-Natta system and pre-polymerized to a defined level, thereby providing a polymer mixture having high molecular weight atactic polypropylene as a micro-molecular mixture.
  • metallocene catalysts having polymerization properties different from those of the classic Ziegler-Natta catalyst being used to produce the UHMWPE would be applicable.
  • Polymer compatibilizers have molecular characteristics and physical properties consisting of the materials to be mixed.
  • a method of the present invention involves impregnating a suitable living syndio-specific polypropylene catalyst into a silica supported transition metal complex (for example, a classic Ziegler-Natta, titanium-impregnated silica or magnesium chloride).
  • a silica supported transition metal complex for example, a classic Ziegler-Natta, titanium-impregnated silica or magnesium chloride.
  • the activated catalyst solution is added in such a manner as to prevent clumping and agglomeration of the material.
  • the dried catalyst mixture is dried and can be stored as such.
  • a phenoxy-imine catalyst containing titanium, zirconium, or hafnium which under normal polymerization conditions polymerizes propylene in predominately syndiotactic sequences, is activated with aluminum alkyl/alumoxane and then added to a pre-formed Ziegler-Natta catalyst.
  • the phenoxy-imine catalyst produces weakly syndiotactic homo-polymers when polymerized in propylene
  • the pre-polymerization using the novel mixture described above is done with propylene to a pre-determined level in bulk, slurry, or gas phase polymerization, followed by polymerization (or co-polymerization) with ethylene or other suitable olefinic monomers.
  • the catalyst system of the present invention prepared above would consist of a polymer matrix consisting of a pre-determined amount of pre-polymerized syndiotactic polypropylene molecular chains having substantial polyethylene block mixed with polyethylene molecular chains.
  • the polyethylene-co-syndiotactic polypropylene block co-polymers would provide anti-fouling properties such as those previously described for pre-polymerized polymers, while also providing a compatibilizing function for the subsequent materials produced by the classic Ziegler-Natta catalyst system.
  • the ethylene can be polymerized to high molecular weight, thereby providing a polymer having properties comparable to those used in arthroscopic application.
  • the properties attained by these polymers would encompass benefits of syndiotactic polypropylene (including greater modulus and flexibility), while improving the toughness and wear resistance normally experienced with UHMWPE.
  • the pre-polymerization process could be made without propylene but rather, alternatively, be made from any olefin for which the catalyst system loaded onto the supporting classic Ziegler-Natta catalyst system is active.
  • combinations of olefins making co- or ter- polymers would impart unique and useful properties to the finished polymer particles including better fusibility and less grain boundary distributions in addition to imparting physical property enhancements.
  • a Ziegler-Natta catalyst may be added to a solution containing activated single site catalyst.
  • the Ziegler-Natta catalyst may be a heterogeneous 5 th generation Ziegler-Natta catalyst.
  • the activated single site catalyst may be 1) a Pd ⁇ -dnmine catalyst, T) pyridine-bisimine-based complexes of iron and cobalt with varying substituents on the imine carbon, 3) Bis(phenoxy-imine) group 4 metal catalyst, 4) Sita catalyst, or combinations thereof.
  • the catalyst system may then be transferred to a polymerization vessel where pre-polymerization is accomplished.
  • the catalyst is typically activated with a small amount of aluminum alkyl or is alkylated then activated with an aromatic boron salt such as tetrakis-pentafluorophenylboron-trityl complex. Then, pre-polymerization monomer mix may be added. Monomers can be added as a gas (such as with propylene, butene, or combinations thereof), a liquid (such as with butadiene, isoprene, decadiene, etc.), or both. Pre-polymerization may be carried out until such time as the desired amount of material is deposited on the catalyst surface.
  • the desired amount is typically between 0.1 to 25.0 g polymer per gram of catalyst and preferably between 0.1 and 0.5 g polymer per gram of catalyst.
  • the catalyst is transferred to polymerization conditions containing suitable olefmic monomer.
  • suitable olefmic monomer may be, for example, ethylene, a mixture of ethylene and propylene, a mixture of ethylene and hexene, or other suitable combinations of olefin, di- olefin or ter-monomer mixtures which provide a product having the desired end properties.
  • the polymerization was carried out under standard conditions: 8O 0 C, 120 min, 80 psi in heptane. 0.78 g TiBAl (3.9 mmol; 1 ml in 10 ml toluene) was used as a scavenger/activator for the Ziegler-Natta catalyst. The polymer was collected from the reactor, dried in vacuo 90 0 C under vacuum for 6 hours.
  • Example 1 All experimental conditions were carried out in the same fashion as Example 1 with the exception of the pre-polymerization step. 58 mg of catalyst was placed in a 20 ml glass vial. Toluene (10 ml) was added. Then, the mixture was cannulated into the polymerization reactor, and the polymerization was carried out as in Example 1.
  • Example 1 having propylene-co-ethylene block co-polymer from the pre-polymerization provided a higher tensile strength than Comparative Example 1.
  • Catalyst Preparation In a flask containing a heterogeneous 5 th generation Ziegler Natta catalyst is added a solution containing a Pd ⁇ -diimine catalyst, an activated single site catalyst (Living Polymerization of Ethylene Using Pd(II)- ⁇ -Diimine Catalysts. Gottfried, A. C; Brookhart, M. Macromolecules 2001, 1140-1142.). The catalyst system is transferred to a polymerization vessel where pre- polymerization is accomplished. The catalyst is activated with a small amount of aluminum alkyl. Then, pre-polymerization monomer mix is added. Monomers are added as a gas with propylene.
  • Pre-polymerization is carried out until about 0.1 g polymer per gram of catalyst is deposited on the catalyst surface. After the pre-polymerization step is completed, the catalyst is transferred to polymerization conditions containing ethylene, an olefmic monomer.
  • Monomers are added as a liquid with isoprene. Pre-polymerization is carried out until 0.5 g polymer per gram of catalyst is deposited on the catalyst surface. After the pre-polymerization step is completed, the catalyst is transferred to polymerization conditions containing a mixture of ethylene and propylene.
  • Monomers are added as both a gas with butane and as a liquid with butadiene. Pre-polymerization is carried out until 25.0 g polymer per gram of catalyst is deposited on the catalyst surface. After the pre-polymerization step is completed, the catalyst is transferred to polymerization conditions containing a mixture of ethylene and hexane.
  • the catalyst is alkylated then activated with tetrakis- pentafluorophenylboron-trityl complex, an aromatic boron salt. Then, pre-polymerization monomer mix is added. Monomers are added as a gas with propylene and butene. Pre- polymerization is carried out until 0.4 g polymer per gram of catalyst is deposited on the catalyst surface. After the pre-polymerization step is completed, the catalyst is transferred to polymerization conditions containing a mixture of ethylene and hexane.
  • the advantages of the present invention are a result of the pre-polymer being made from a living catalyst and produced as a macromolecular chain having a block structure being compatible with the buly polymerization polymer. Reactor fouling is reduced, and the pre- polymerization polymer has preformed compatibilizer with less tendency to phase separate than heterogeneous polymer systems made without the benefit of this system.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

L'invention porte sur un système de catalyseur qui comprend un catalyseur hétérogène et un catalyseur à site unique imprégné sur la surface du catalyseur hétérogène. A partir de ce système de catalyseur, un catalyseur de polyoléfine prépolymérisé peut être produit par activation du système de catalyseur, ajout d'un mélange de monomère de prépolymérisation, et prépolymérisation du système de catalyseur avec le mélange de monomères de prépolymérisation jusqu'à ce que 0,1 à 25,0 grammes de polymère par gramme de catalyseur soient déposés sur la surface de catalyseur. Un polymère est préparé par polymérisation du catalyseur prépolymérisé avec un monomère oléfinique.
PCT/US2008/085484 2007-12-05 2008-12-04 Mélange de copolymère à blocs polyéthylène-co-polypropylène syndiotactique et polyéthylène d'ultrahaute masse moléculaire Ceased WO2009076152A1 (fr)

Applications Claiming Priority (2)

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US99259907P 2007-12-05 2007-12-05
US60/992,599 2007-12-05

Publications (1)

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WO2009076152A1 true WO2009076152A1 (fr) 2009-06-18

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010027728A1 (fr) * 2008-08-26 2010-03-11 Dsm Ip Assets B.V. Composite de polymère de polyéthylène avec un composant d’homopolymère de pe et un composant de copolymère de pe
CN101864010A (zh) * 2010-06-21 2010-10-20 北京大学 双金属催化剂前体及其在烯烃聚合或共聚合中的应用
JP2011122145A (ja) * 2009-11-13 2011-06-23 Mitsui Chemicals Inc オレフィン重合用触媒およびオレフィン重合体の製造方法
CN108084312A (zh) * 2017-11-24 2018-05-29 新疆天利高新石化股份有限公司 预聚合法制备高丁烯含量的丙烯—丁烯共聚物的方法
CN112638958A (zh) * 2018-07-19 2021-04-09 博里利斯股份公司 制备uhmwpe均聚物的方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6492293B1 (en) * 1999-11-12 2002-12-10 Bp Chemicals Limited Polymerisation catalyst
EP1650230A1 (fr) * 2004-10-21 2006-04-26 Total Petrochemicals Research Feluy Polyoléfines préparées par un système catalytique comprenant un Ziegler-Natta et un metallocène dans un réacteur unique

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6492293B1 (en) * 1999-11-12 2002-12-10 Bp Chemicals Limited Polymerisation catalyst
EP1650230A1 (fr) * 2004-10-21 2006-04-26 Total Petrochemicals Research Feluy Polyoléfines préparées par un système catalytique comprenant un Ziegler-Natta et un metallocène dans un réacteur unique

Non-Patent Citations (2)

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Title
ATSUSHI SAKUMA, MARC-STEPHAN WEISER AND TERUNORI FUJITA,, POLYM. J, vol. 39, 24 January 2007 (2007-01-24), pages 193 - 207, XP002517369 *
BIANCHINI, CLAUDIO; MILLER, HAMISH; CIARDELLI, FRANCESCO: "Combinations of transition metal catalysts for reactor blending", 2004, SPRINGER NETHERLANDS, XP009113019, 175 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010027728A1 (fr) * 2008-08-26 2010-03-11 Dsm Ip Assets B.V. Composite de polymère de polyéthylène avec un composant d’homopolymère de pe et un composant de copolymère de pe
JP2011122145A (ja) * 2009-11-13 2011-06-23 Mitsui Chemicals Inc オレフィン重合用触媒およびオレフィン重合体の製造方法
CN101864010A (zh) * 2010-06-21 2010-10-20 北京大学 双金属催化剂前体及其在烯烃聚合或共聚合中的应用
CN108084312A (zh) * 2017-11-24 2018-05-29 新疆天利高新石化股份有限公司 预聚合法制备高丁烯含量的丙烯—丁烯共聚物的方法
CN112638958A (zh) * 2018-07-19 2021-04-09 博里利斯股份公司 制备uhmwpe均聚物的方法
CN112638958B (zh) * 2018-07-19 2023-06-02 博里利斯股份公司 制备uhmwpe均聚物的方法
US11680114B2 (en) 2018-07-19 2023-06-20 Borealis Ag Process for the preparation of an UHMWPE homopolymer
US11965052B2 (en) 2018-07-19 2024-04-23 Borealis Ag Process for the preparation of an UHMWPE homopolymer

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