WO2004046210A1 - Catalyseurs et procede pour la production d'esters polyvinyliques - Google Patents

Catalyseurs et procede pour la production d'esters polyvinyliques Download PDF

Info

Publication number
WO2004046210A1
WO2004046210A1 PCT/EP2003/012539 EP0312539W WO2004046210A1 WO 2004046210 A1 WO2004046210 A1 WO 2004046210A1 EP 0312539 W EP0312539 W EP 0312539W WO 2004046210 A1 WO2004046210 A1 WO 2004046210A1
Authority
WO
WIPO (PCT)
Prior art keywords
different
same
formula
group
hydrogen
Prior art date
Application number
PCT/EP2003/012539
Other languages
German (de)
English (en)
Inventor
Uwe Blank
Tim Dickner
Jörg SCHOTTEK
Jörg Ludwig SCHULTE
Original Assignee
Celanese Ventures Gmbh
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 Celanese Ventures Gmbh filed Critical Celanese Ventures Gmbh
Publication of WO2004046210A1 publication Critical patent/WO2004046210A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/04—Nickel compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/006—Palladium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/006—Palladium compounds
    • C07F15/0066—Palladium compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/04—Nickel compounds
    • C07F15/045—Nickel compounds without a metal-carbon linkage
    • 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
    • C08F18/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F18/02—Esters of monocarboxylic acids
    • C08F18/04—Vinyl esters

Definitions

  • Catalysts for the production of polyvinyl esters and a process for the production of polyvinyl esters.
  • the present invention relates to a novel compound which can be used as a catalyst in the polymerization and copolymerization of vinyl esters and to a process for the polymerization and copolymerization of vinyl ester using these compounds.
  • Vinyl esters are olefinic compounds with the following basic structure.
  • Polyvinyl esters are polymers accessible from vinyl esters by olefinic polymerization, of which the polyvinyl acetates have by far the greatest technical importance.
  • Polyvinyl acetate is an important thermoplastic polymer and is used, among other things, as an adhesive (component), paint raw material, for packaging films, for the coating of paper and food (sausage and cheese coatings), as an additive for concrete and as a raw material for the production of polyvinyl alcohols and polyvinyl acetals used (Römpp Lexikon Chemie - Version 2.0, Stuttgart / New York: Georg Thieme Verlag 1999).
  • polyvinyl acetate is produced by free radical polymerizations, the polymerization being able to be carried out in solution, in bulk and in emulsion.
  • Azoisobutyronitrile and dibenzoyl peroxide (AIBN / BPO) are mainly used as radical initiators. Because this radical
  • ARP atom transfer radical polymerization
  • a transition metal catalyzed insertion polymerization with so-called metallocene or post-metallocene contrast enables the synthesis of stereospecific polymers having a narrow molecular weight distribution (W. Kaminsky in Ullmann's Encyclopedia of Industrial Chemistry, 6 th Ed., 2002 Electronic Release, Wiley / VCH).
  • This method has been used successfully for many mostly simple ⁇ -olefins. With this method, the use of polar monomers has hitherto been restricted to a few acrylates (WO0121670). However, the polymerization of vinyl acetate by a transition metal-catalyzed insertion polymerization with metallocenes or post-metallocenes has so far not been possible.
  • the present invention relates to compounds of the formula I.
  • M 1 is a transition metal from group 8 to 10 in oxidation state 0, preferably nickel or palladium, and m is the same or different and an integer between 1 and 4 and is the same or different , and an integer between 1 and 4, and
  • L 1 is in each case identical or different and has a mono- or bidentate ligand
  • Is donor atoms of the 14th to 16th group of elements preferably of the following basic structure
  • R 1 is in each case the same or different, and is hydrogen or a Ci - C 20
  • R 2 is in each case the same or different, and is hydrogen or a Ci - C 20
  • R 3 is in each case the same or different, and is hydrogen or a Ci - C 20
  • - is a carbon-containing group and can also form a cyclic system with R 4 or R 5 , and
  • R 4 is in each case the same or different, and is hydrogen or a Ci - C 20
  • - is a carbon-containing group and can also form a cyclic system with R 3 or R 5 , and
  • R 5 is in each case the same or different, and is hydrogen or a Ci - C 2 n
  • - is carbon-containing group, and can also form a cyclic system with R 3 or R 4 , and o is 0, 1 or 2, and p is 0, 1 or 2, and q is an integer from 0 to 20 , preferably 0 to 10 and particularly preferably 0, 1 or 2, and r is the same or different and is 1 or 2, and s is the same or different and is 1 or 2, and t is the same or is different and is 1 or 2, and
  • A is the same or different, and has the following basic structure
  • R 6 is the same or different, and is hydrogen, or a halogen atom, or a C- ⁇ - C 2 o- carbon-containing group
  • R 7 is the same or different, and is hydrogen, or a halogen atom, or a Ci - C 2 o- carbon-containing group
  • R 1 and R 2 can also form a cyclic system, and u are each the same or different and are either one or two, and v are each the same or different and are either one or two, except for the compound of formula X.
  • Ci in the context of the present invention
  • - C 2 o carbon-containing group is preferably the radicals CC 2 -alkyl, particularly preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl , t-butyl, n-pentyl, s-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-octyl or cyclooctyl, Ci - C 20 - alkenyl, particularly preferably ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, Octenyl or cyclooctenyl, Ci - C 2 o - alkynyl, particularly preferably ethynyl, propynyl, but
  • Aryl particularly preferably phenyl, biphenyl, naphthyl, anthracenyl, triphenylenyl, [1, V; 3 ', V'] terpheny ⁇ -2'- ⁇ , binaphthyl or phenanthrenyl, C 6 -C 20 -fluoroaryl, particularly preferably tetrafluorophenyl or heptafluoronaphthyl , CrC 20 alkoxy, particularly preferably methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy or t-butoxy, C 6 -C 2 o-aryloxy, particularly preferably phenoxy, naphthoxy .
  • Acetyl, acetoxy or nitrile understood, where one or more C 1 -C 20 carbon-containing groups can form a cyclic system.
  • preferred olefinic ligands A are styrene, norbornene, butadiene, cyclooctadiene, cyclohexene, vinyl acetate, methyl acrylate, methyl methacrylate,
  • Acrylic acid ethyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate are used.
  • the compound of formula X is from J. Organomet. Chem. 1989, 367, 233-242, already known.
  • the synthesis described there is also suitable for the preparation of the compounds of the formula I according to the invention and can be illustrated using the example below:
  • the compounds of formula I are as catalysts in the o ymer sat on of
  • Another object of the present invention is a process for the polymerization of vinyl esters using the compounds according to the invention, wherein both the homopolymerization of
  • Vinyl esters as well as the copolymerization of vinyl esters with other olefins is understood.
  • olefins having 2 to 20, preferably 2 to 10, carbon atoms, such as ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-decene, 4-methyl-1-pentene or 1-octene, styrene, dienes such as 1,3-butadiene, 1,4-hexadiene, vinyl norbornene,
  • Norbornadiene, ethylnorbornadiene and cyclic olefins such as norbornene, cyclopentadiene, tetracyclododecene or methylnorbornene, and polar monomers such as methyl acrylate, methyl methacrylate, acrylic acid, ethyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate.
  • vinyl acetate is preferably homopolymerized, or vinyl acetate is copolymerized with one or more 1-olefins having 2 to 8 carbon atoms, such as ethene, propene, styrene, norbornene, methyl acrylate, methyl methacrylate, acrylic acid or butadiene.
  • 1-olefins having 2 to 8 carbon atoms, such as ethene, propene, styrene, norbornene, methyl acrylate, methyl methacrylate, acrylic acid or butadiene.
  • the polymerization is carried out at a temperature of from -20 to 300.degree. C., preferably from -20 to 200.degree. C., very particularly preferably at from -20 to 100.degree.
  • the pressure is 0.5 to 2000 bar, preferably 1 to 64 bar.
  • the polymerization can be in solution, in Mass, in suspension or in emulsion, continuously or discontinuously, one or more stages.
  • Suitable solvents for the polymerization are, for example, aliphatic hydrocarbons such as pentane, hexane and the like or aromatic hydrocarbons such as benzene, toluene, xylenes and the like, or ethers such as diethyl ether, dibutyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane, anisole, diphenyl ether and Ethylphenyl ether, including halogenated solvents such as dichloromethane, trichloromethane, chlorobenzene, bromobenzene and the like, as well as ethyl acetate, acetone, N, N-dimethylformamide, ethylene carbonate, methanol, ethanol, propanol, i-propanol or water. Mixtures of different solvents in different solvents can also be used
  • Ratios are used according to the invention.
  • additional cocatalysts or additives can be used in the process described to improve activities and to change tacticities in the polymer.
  • Preferred cocatalysts or additives are compounds of the formula II
  • M 2 is in each case the same or different and is a metal from the 1st to 14th group of the periodic table, preferably lithium, magnesium, scandium, titanium, boron, aluminum, silicon, tin, particularly preferably boron and aluminum, and R 9 is the same or different and is hydrogen, a halogen atom or a Ci
  • the cocatalysts or additives of the formula II used according to the invention are one or more compounds of the type of an aluminoxane and / or another Lewis acid.
  • Cocatalysts which can form the catalyst system together with a transition metal complex of the formula I according to the invention are particularly preferred.
  • this catalyst system contains at least one compound of the formula II of the aluminoxane or Lewis acid type.
  • Suitable cocatalysts which can form the catalyst system according to the invention together with a compound of the formula I are described in WO 0148034.
  • the catalyst systems according to the invention, which can be formed from a compound of the formula I and the cocatalysts described in WO 0148034, are also included in the present invention.
  • aluminoxanes which are described, for example, in JACS 1 17 (1995), 6465-74 and Organometallics 13 (1994), 2957-2969 , or Lewis acids, which consist for example of boron or organoaluminum compounds, or
  • Lewis acids which are optionally used are those which contain at least one or more atoms of lithium, magnesium, scandium, titanium,
  • organoboron or organoaluminum compound which contains C1-C20- carbon-containing groups, such as branched or unbranched alkyl or haloalkyl, such as e.g. Methyl, propyl, isopropyl, isobutyl, trifluoromethyl, unsaturated groups, such as aryl or haloaryl, such as phenyl, tolyl, benzyl groups, p-
  • Fluorophenyl 3,5-difluorophenyl, pentachlorophenyl, pentafluorophenyl, 3,4,5-trifluorophenyl and 3,5-di (thfluoromethyl) phenyl.
  • optionally used cocatalysts are:
  • Trifluoroborane triphenylborane, tris (4-fluorophenyl) borane, tris (3,5-difluorophenyl) borane, tris (4-fluoromethylphenyl) borane,
  • Tris (3,5-difluorophenyl) borane tris (3,4,5-trifluorophenyl) borane.
  • the carrier component of the catalyst system according to the invention can be any organic or inorganic, inert solid, in particular a porous carrier such as talc, inorganic oxides and finely divided polymer powders (e.g. highly porous polyolefins such as polyethylene, polypropylene, polystyrenes, copolymers, or polar polymers such as e.g.
  • Polyurethanes polymethacrylates, polymethyl methacrylates, polyvinyl acetate, polyacrylonitrile, polyethylene glycol or copolymers).
  • Suitable inorganic oxides can be found in ll.-VI. Main group of the periodic table and the lll.-IV. Subgroup of the Periodic Table of the Elements.
  • preferred oxides as carriers include silicon dioxide, hydrotalcite, aluminum oxide, and mixed oxides of the elements calcium, aluminum, silicon, magnesium, titanium and corresponding oxide mixtures.
  • Other inorganic oxides that can be used alone or in combination with the last-mentioned preferred oxidic supports are, for example, MgO, ZrO 2 , TiO 2 or B 2 O 3 , to name just a few. The invention is illustrated by the following examples which, however, do not restrict the invention.

Landscapes

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

Abstract

L'invention concerne de nouveaux composés pouvant être utilisés comme catalyseur et/ou système de catalyseur lors de la polymérisation et de la copolymérisation d'esters vinyliques. L'invention concerne également un procédé pour la polymérisation et la copolymérisation d'esters vinyliques au moyen desdits composés.
PCT/EP2003/012539 2002-11-20 2003-11-11 Catalyseurs et procede pour la production d'esters polyvinyliques WO2004046210A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10254094.2 2002-11-20
DE2002154094 DE10254094A1 (de) 2002-11-20 2002-11-20 Katalysatoren zur Herstellung von Polyvinylestern und ein Verfahren zur Herstellung von Polyvinylestern

Publications (1)

Publication Number Publication Date
WO2004046210A1 true WO2004046210A1 (fr) 2004-06-03

Family

ID=32308602

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2003/012539 WO2004046210A1 (fr) 2002-11-20 2003-11-11 Catalyseurs et procede pour la production d'esters polyvinyliques

Country Status (2)

Country Link
DE (1) DE10254094A1 (fr)
WO (1) WO2004046210A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0824111A1 (fr) * 1996-08-12 1998-02-18 Elf Atochem S.A. Procédé de polymérisation ou copolymérisation radicalaire contrÔlée de monomères (méth)acryliques et vinyliques et (co)polymères obtenus
WO2001021670A1 (fr) * 1999-09-20 2001-03-29 The Penn State Research Foundation Polymerisation de norbornene et d'acrylatescatalysee par le palladium(ii)

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0824111A1 (fr) * 1996-08-12 1998-02-18 Elf Atochem S.A. Procédé de polymérisation ou copolymérisation radicalaire contrÔlée de monomères (méth)acryliques et vinyliques et (co)polymères obtenus
WO2001021670A1 (fr) * 1999-09-20 2001-03-29 The Penn State Research Foundation Polymerisation de norbornene et d'acrylatescatalysee par le palladium(ii)

Also Published As

Publication number Publication date
DE10254094A1 (de) 2004-06-09

Similar Documents

Publication Publication Date Title
DE60014376T2 (de) Katalysatoren, die n-pyrrolylsubstituierte stickstoffdonoren enthalten
DE69817357T2 (de) Katalysator für die herstellung von olefinpolymeren
DE69334188T2 (de) Verfahren zur Herstellung von einem geträgertem Aktivatorkomponenten
EP1945681B1 (fr) Procede de production de polymeres de poids moleculaire tres eleve au moyen de catalyseurs metallocenes pontes speciaux
DE69919755T2 (de) Katalysator zur ethylen homo und copolymerisation
EP1204685B1 (fr) Copolymeres d'ethylene et d'alpha-olefines c3-c9
DE2404961A1 (de) Alternierende copolymerisate mit funktionellen gruppen, verfahren zu ihrer herstellung und ihre verwendung zur herstellung von geformten gebilden, als bindemittel in anstrichmitteln und klebstoffkomponenten
KR101703274B1 (ko) 메탈로센 화합물, 이를 포함하는 촉매 조성물 및 이를 이용한 올레핀 중합체의 제조방법
DE69915626T2 (de) Durch ein Kohlenstoffatom verbundene Biscyclopentadienylverbindungen und darmit hergestellte Metallocene
DE2721263A1 (de) Verfahren zur herstellung eines zieglerkatalysators
EP1771484A1 (fr) Procede de production de polymeres de poids moleculaire ultra eleve a l'aide de catalyseurs metallocene non pontes
WO2001007491A1 (fr) Procede pour preparer des (co)polymeres d'olefines
DE3003327C2 (fr)
DE60212392T2 (de) Katalysator zur polymerisation und copolymerisation von ethylen
EP1284981A2 (fr) Procede de preparation de composes de metal de transition et leurs utilisation pour polymeriser des olefines
US5556822A (en) Catalyst system for polyermization of olefin
WO2004046210A1 (fr) Catalyseurs et procede pour la production d'esters polyvinyliques
DE60212407T2 (de) Katalysator für die polymerisation und copolymerisation von ethylen
DE60031724T2 (de) Katalysator zur ethylen homo- und copolymerisation
WO2004046209A1 (fr) Catalyseurs de metal de transition pour produire des polyvinylesters
EP1539842A1 (fr) Nouveaux esters polyvinyliques
DE2700163C2 (fr)
EP1992630B1 (fr) Composés non metallocènes fixés de façon covalente, procédé de fabrication de ceux-ci et utilisation pour la polymerisation
EP1336613B1 (fr) Complexes métalliques à base d'acide iminohydroxamique
DE60102789T2 (de) Olefinpolymerisationskatalysatoren

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): BR CA CN ID JP KR MX US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP