WO2014060252A1 - Procédé pour la synthèse de polyéthylène de masse moléculaire très élevée (pe-hpm) démêlé utilisant un catalyseur au cr ou au ti - Google Patents

Procédé pour la synthèse de polyéthylène de masse moléculaire très élevée (pe-hpm) démêlé utilisant un catalyseur au cr ou au ti Download PDF

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Publication number
WO2014060252A1
WO2014060252A1 PCT/EP2013/071017 EP2013071017W WO2014060252A1 WO 2014060252 A1 WO2014060252 A1 WO 2014060252A1 EP 2013071017 W EP2013071017 W EP 2013071017W WO 2014060252 A1 WO2014060252 A1 WO 2014060252A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
added
polymer
uhmw
reaction vessel
Prior art date
Application number
PCT/EP2013/071017
Other languages
English (en)
Inventor
Dario Romano
Sara Ronca
Johan BOS
Sanjay Rastogi
Original Assignee
Teijin Aramid B.V.
Loughborough University
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 Teijin Aramid B.V., Loughborough University filed Critical Teijin Aramid B.V.
Priority to US14/424,338 priority Critical patent/US20150224448A1/en
Publication of WO2014060252A1 publication Critical patent/WO2014060252A1/fr

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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
    • 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
    • C08F2420/00—Metallocene catalysts
    • C08F2420/01—Cp or analog bridged to a non-Cp X neutral donor

Definitions

  • the objective of present invention is achieved with a process for the manufacture of disentangled ultra-high molecular weight polyethylene in the presence of a co- catalyst and a catalyst which is a substituted monocyclopentadienyl, monoindenyl, monofluorenyl or heterocyclopentadienyl complex of chromium or titanium in which at least one of the substituents on the cyclopentadienyl ring carries a neutral donor function which is bonded rigidly, not exclusively via sp 3 -hybridized carbon or silicon atoms, characterized in that the process comprises the following steps in the given order:
  • This invention also pertains to disentangled UHMW-PE obtainable by the polymerization process according to this invention. All embodiments described for the polymerization process according to this invention are also applicable to the polymer produced by these processes and for any product comprising the polymer produced according to present process.
  • the disentangled UHMW-PE of this invention is characterized by a number average molecular weight of at least 0.5 million g/mol, preferably at least 3 million g/mol. The weight average molecular weight ranges above 1 million g/mol and preferably ranges between 1 to 20 million g/mol.
  • the weight average molecular weight is defined as:
  • comparative sample 1 (CE1 ) 0.75 I of anhydrous toluene was introduced into the reactor vessel under nitrogen stream and continuous stirring at 1500 rpm was applied. 1 .5 g of BHT was dissolved in 10 ml of MAO (co-catalyst) and was allowed to react for 30 minutes. Subsequently, 8 ml of the reacted solution was introduced into the reactor and 2 ml of the reacted solution was used to dissolve 6.0 mg of catalyst in combination with 8 ml of toluene, the resulting solution was stirred for 5 minutes under magnetic stirring and then injected into the reactor. After a polymerization time of 60 minutes at 10°C, the reaction was quenched by addition of methanol.
  • MAO co-catalyst

Landscapes

  • Chemical & Material Sciences (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 procédé pour la fabrication de polyéthylène de masse moléculaire très élevée démêlé, en présence d'un cocatalyseur comprenant du trialkylaluminium et d'un catalyseur qui est un complexe de monocyclopentadiényle substitué, de monoindényle, de monofluorényle ou d'hétérocyclopentadiényle du chrome ou du titane, au moins l'un des substituants sur le noyau cyclopentadiényle portant une fonction donneuse neutre qui est liée de façon rigide, non exclusivement par l'intermédiaire d'atomes de carbone ou de silicium hybridés sp3, caractérisé en ce que le procédé comprend les étapes suivantes dans l'ordre donnée : i) un solvant et un fixateur trialkylaluminium et éventuellement du cocatalyseur sont ajoutés à un réacteur, ii) de l'éthylène est ajouté au réacteur et iii) un mélange du catalyseur et du cocatalyseur est ajouté au réacteur. L'invention porte également sur du PE-hpm pouvant être obtenu par ce procédé, ainsi que sur des fibres, des films, des rubans et des moulages comprenant ce matériau et sur leur utilisation dans des articles résistants à la pénétration, des gants, des films bi-orientés, des câbles, des élingues, des cordes, des filets, des tuyaux et des prothèses.
PCT/EP2013/071017 2012-10-09 2013-10-09 Procédé pour la synthèse de polyéthylène de masse moléculaire très élevée (pe-hpm) démêlé utilisant un catalyseur au cr ou au ti WO2014060252A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US14/424,338 US20150224448A1 (en) 2012-10-09 2013-10-09 Process for concentrating at least one chemical from liquid or gaseous mixtures

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP12188698.0 2012-10-16
EP12188698 2012-10-16

Publications (1)

Publication Number Publication Date
WO2014060252A1 true WO2014060252A1 (fr) 2014-04-24

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Application Number Title Priority Date Filing Date
PCT/EP2013/071017 WO2014060252A1 (fr) 2012-10-09 2013-10-09 Procédé pour la synthèse de polyéthylène de masse moléculaire très élevée (pe-hpm) démêlé utilisant un catalyseur au cr ou au ti

Country Status (1)

Country Link
WO (1) WO2014060252A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109096423A (zh) * 2018-10-30 2018-12-28 宁波大学 低缠结超高分子量聚烯烃的制备方法
CN112521536A (zh) * 2020-11-18 2021-03-19 浙江大学 一种制备超高分子量解缠绕聚乙烯的聚合方法及其装置

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001012641A1 (fr) 1999-08-13 2001-02-22 Basell Polyolefine Gmbh Complexes de monocyclopentadienyle contenant du chrome, du molybdene ou du tungstene et comportant un pont donneur
US6919412B1 (en) 1999-08-13 2005-07-19 Basell Polyolefine Gmbh Monocyclopentadienyl complexes of chromium, molybdenum or tungsten with a donor bridge
DE102006051721A1 (de) * 2006-10-30 2008-05-15 Basell Polyolefine Gmbh Verfahren zur Polymerisation von Olefinen mit Organoübergangsmetallkomplex basierten Katalysatorsystemen
WO2009007045A1 (fr) 2007-07-09 2009-01-15 Teijin Aramid B.V. Film de polyéthylène de haute résistance à la traction et à énergie de rupture élevée par traction
WO2010079172A1 (fr) 2009-01-09 2010-07-15 Teijin Aramid B.V. Film de polyéthylène ayant une résistance à la traction élevée et une énergie de rupture par traction élevée
WO2010079174A2 (fr) 2009-01-09 2010-07-15 Teijin Aramid B.V. Film de polyéthylène et son procédé de fabrication
DE102009023651A1 (de) 2009-05-26 2010-12-02 Aesculap Ag Mit einem Stabilisator dotiertes Polyethylen
WO2011054927A1 (fr) 2009-11-06 2011-05-12 Dsm Ip Assets B.V. Composant de catalyseur pour la polymérisation d'oléfines ayant un ligand guanidinate
US7956140B2 (en) 2004-03-17 2011-06-07 Dsm Ip Assets B.V. Polymerization catalyst comprising amidine ligand
WO2012139934A1 (fr) 2011-04-13 2012-10-18 Dsm Ip Assets B.V. Fibre d'uhmwpe à comportement au fluage optimisé

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6437161B1 (en) 1999-08-13 2002-08-20 Basf Aktiengesellschaft Monocyclopentadienyl complexes of chromium, molybdenum or tungsten
US6699948B2 (en) 1999-08-13 2004-03-02 Basf Aktiengesellschaft Monocyclopentadienyl complexes of chromium, molybdenum or tungsten
US6787498B2 (en) 1999-08-13 2004-09-07 Basell Polyolefine Gmbh Monocyclopentadienyl complexes of chromium, molybdenum or tungsten
US6838563B2 (en) 1999-08-13 2005-01-04 Basell Polyolefins Monocyclopentadienyl complexes of chromium, molybdenum or tungsten
US6919412B1 (en) 1999-08-13 2005-07-19 Basell Polyolefine Gmbh Monocyclopentadienyl complexes of chromium, molybdenum or tungsten with a donor bridge
WO2001012641A1 (fr) 1999-08-13 2001-02-22 Basell Polyolefine Gmbh Complexes de monocyclopentadienyle contenant du chrome, du molybdene ou du tungstene et comportant un pont donneur
US7956140B2 (en) 2004-03-17 2011-06-07 Dsm Ip Assets B.V. Polymerization catalyst comprising amidine ligand
DE102006051721A1 (de) * 2006-10-30 2008-05-15 Basell Polyolefine Gmbh Verfahren zur Polymerisation von Olefinen mit Organoübergangsmetallkomplex basierten Katalysatorsystemen
WO2009007045A1 (fr) 2007-07-09 2009-01-15 Teijin Aramid B.V. Film de polyéthylène de haute résistance à la traction et à énergie de rupture élevée par traction
WO2010079172A1 (fr) 2009-01-09 2010-07-15 Teijin Aramid B.V. Film de polyéthylène ayant une résistance à la traction élevée et une énergie de rupture par traction élevée
WO2010079174A2 (fr) 2009-01-09 2010-07-15 Teijin Aramid B.V. Film de polyéthylène et son procédé de fabrication
DE102009023651A1 (de) 2009-05-26 2010-12-02 Aesculap Ag Mit einem Stabilisator dotiertes Polyethylen
WO2011054927A1 (fr) 2009-11-06 2011-05-12 Dsm Ip Assets B.V. Composant de catalyseur pour la polymérisation d'oléfines ayant un ligand guanidinate
WO2012139934A1 (fr) 2011-04-13 2012-10-18 Dsm Ip Assets B.V. Fibre d'uhmwpe à comportement au fluage optimisé

Non-Patent Citations (9)

* Cited by examiner, † Cited by third party
Title
BLITZ; MCFADDIN, JOURNAL OF APPLIED POLYMER SCIENCE, vol. 51, 1994, pages 13 - 20
MACOSKO: "Rheology: Principles, Measurements and Applications", 1994, WILEY- VCH
MARK ET AL., ANGEW. CHEM. INT. ED., vol. 49, 2010, pages 8751 - 8754
PANDEY ET AL., MACROMOLECULES, vol. 44, 2011, pages 4952 - 4960
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SARA RONCA ET AL: "Improving the performance of a catalytic system for the synthesis of ultra high molecular weight polyethylene with a reduced number of entanglements", ADVANCES IN POLYMER TECHNOLOGY, vol. 31, no. 3, 1 September 2012 (2012-09-01), pages 193 - 204, XP055052080, ISSN: 0730-6679, DOI: 10.1002/adv.21265 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109096423A (zh) * 2018-10-30 2018-12-28 宁波大学 低缠结超高分子量聚烯烃的制备方法
CN109096423B (zh) * 2018-10-30 2020-12-15 宁波大学 低缠结超高分子量聚烯烃的制备方法
CN112521536A (zh) * 2020-11-18 2021-03-19 浙江大学 一种制备超高分子量解缠绕聚乙烯的聚合方法及其装置

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