WO2004046209A1 - Catalyseurs de metal de transition pour produire des polyvinylesters - Google Patents

Catalyseurs de metal de transition pour produire des polyvinylesters Download PDF

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Publication number
WO2004046209A1
WO2004046209A1 PCT/EP2003/012538 EP0312538W WO2004046209A1 WO 2004046209 A1 WO2004046209 A1 WO 2004046209A1 EP 0312538 W EP0312538 W EP 0312538W WO 2004046209 A1 WO2004046209 A1 WO 2004046209A1
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WIPO (PCT)
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group
different
formula
same
integer
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PCT/EP2003/012538
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German (de)
English (en)
Inventor
Tim Dickner
Jörge SCHOTTEK
Jörg Ludwig SCHULTE
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Celanese Ventures Gmbh
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Publication of WO2004046209A1 publication Critical patent/WO2004046209A1/fr

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    • 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 System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System 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 System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System 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 System
    • 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 System
    • 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

  • Transition metal catalysts for the production of polyvinyl esters are Transition metal catalysts for the production of polyvinyl esters
  • the present invention relates to catalysts for polymerization
  • Copolymerization of vinyl esters and a process for the polymerization and copolymerization of vinyl esters.
  • 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 are by far the largest technical
  • Polyvinyl acetate is an important thermoplastic polymer and is used, among other things, as an adhesive (component), raw material for coatings, for packaging films, for the coating of paper and food (sausage and cheese coatings)
  • 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. Since these radical polymerizations take place quickly and in an uncontrolled manner, stereodifferentiation is ruled out and control of the molecular weight and the molecular weight distribution very difficult (W. Daniels in.. Kirk-Othmer encycl Chem Technol, 3rd Ed 1983, 23, 817-847.).
  • the transition metal allows catalyzed insertion polymerization with so-called metallocene or post-metallocene 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).
  • catalysts with a suitable ligand structure have now been found which not only permit the simple insertion of vinyl esters, but also multiple insertion up to the formation of the polymer.
  • the present invention relates to compounds of the formula I.
  • M 1 is a transition metal of the 3rd to 12th group of the periodic table of the
  • Elements means whose oxidation state is not equal to zero, preferably the 8th to 10th group, particularly preferably nickel or palladium, and
  • R 1 is hydrogen or a Ci - C 2 o- carbon-containing group or
  • R 2 is hydrogen or a Ci - C 2 o- carbon-containing group or
  • Is halogen and is an integer between 1 and 4, and is 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
  • X 1 is in each case the same or different, and is an element from the 14th to 16th group of elements, particularly preferably nitrogen or phosphorus, and
  • X 2 is in each case the same or different, and an element of the 14th to 16th group of the elements, particularly preferably nitrogen or phosphorus, and R 3 is in each case the same or different, and is hydrogen or a Ci - C 2 o
  • X 1 is a carbon-containing group, and when X 1 is nitrogen preferably a substituted arylidene or aryl group or when X 1 is phosphorus preferably a substituted aryl group and
  • R 4 is in each case the same or different, and is hydrogen or a Ci - C 2 o - carbon-containing group, and if X 2 is nitrogen preferably a substituted arylidene or aryl group or if X 2 is phosphorus preferably a substituted aryl group Is group and R 5 is in each case the same or different, and is hydrogen or a Ci - C 2 o
  • - is a carbon-containing group and can also form a cyclic system with R 6 or R 7 , and
  • R 6 is in each case the same or different, and is hydrogen or a Ci - C 2 o
  • - is a carbon-containing group and can also form a cyclic system with R 5 or R 7 , and
  • R 7 is in each case identical or different and is hydrogen or a Ci - C 2 o - carbon-containing group, and can also form a cyclic system with R 5 or R 6 , and m is 0, 1 or 2, and n is equal Is 0, 1 or 2, and o is an integer from 0 to 20, preferably 0 to 10 and particularly preferably is 0, 1 or 2, and p is in each case identical or different and is 1 or 2, and q is the same or different and is 1 or 2, and r is the same or different and is 1 or 2.
  • Ci in the context of the present invention
  • - C 2 o carbon-containing group is preferably the radicals -C 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 2 o - alkenyl, particularly preferably ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, Cyclohexenyl, octenyl or cyclooctenyl, Ci - C 2 o - alkynyl, particularly preferably ethynyl, propyn
  • C 4 -C 2 o-heterocycloalkyl particularly preferably furyl, benzofuryl, 2-pyrolidinyl, 2-indolyl, 3-indolyl, 2,3-dihydroindolyl, C 8 -C 2 o-arylalkenyl, particularly preferably o-vinylphenyl, m- vinylphenyl, p-vinylphenyl, C 8 -C 2 o-arylalkynyl, particularly preferably o-ethynylphenyl, m-ethynylphenyl or p-ethynylphenyl, C 2 - C 2 o - heteroatom-containing group, particularly preferably carbonyl, benzoyl, oxybenzoyl, benzoyloxy, acetyl .
  • Acetoxy or nitrile understood, where one or more C 1 -C 2 o-carbon-containing groups can form a cyclic system.
  • n 1 -5
  • Ph may be the same or different and may be a phenyl, a substituted phenyl group such as tolyl or methoxyphenyl, a fluorinated phenyl, or an oxyphenyl, or another substituted aromatic radical and can also be an alkyl or oxyalkyl radical.
  • iodaniline is reacted with diphenylphosphine to form the corresponding aminoarylphosphino compound under palladium catalysis.
  • the corresponding ligand is then built up in a condensation reaction with a benzaldehyde derivative, which is then reacted directly with the desired metal species to form a catalyst according to the invention.
  • the compounds of the formula I according to the invention are suitable as catalysts for the preparation of polyvinyl esters.
  • Another component of the present invention are compounds of formula II, which is formed from a compound of formula I by conversion with vinyl esters.
  • R 8 is the same or different and is hydrogen or a Ci - C 2 o- carbon-containing group
  • R 9 is hydrogen or a Ci - C 2 o - carbon-containing group
  • X 3 is a non-coordinating anion
  • s is either an integer 1 or 2
  • t is an integer between 1 and 3
  • u is an integer between 1 and 3
  • v is an integer between 1 and 3
  • w is a is an integer between 1 and 3 where t multiplied by u is always equal to v multiplied by w, and the other radicals have the meaning defined under formula I, except for the compound of formula A.
  • X 3 preferably means those composed of mixtures of several atoms of the elements aluminum, boron, antimony, arsenic, nitrogen, carbon, phosphorus, sulfur, oxygen, chlorine and fluorine. In the context of this invention, this is particularly preferably understood to mean fluorinated or perfluorinated Ci - C 2 o -carbon-containing groups.
  • Illustrative, but not limiting, examples of this are: tetraphenylborate, tetrafluoroborate, tetrakis (pentafluorophenyl) borate, tetrakis (dimethylphenyl) borate, tetrakis (tolyl) borate, tetrakis (3,5-bis-trifluoromethylphenyl) borate, tetrakis (tetrakis) , Tetrakis (4-fluorophenyl) borate, tetrakis (pentafluoropheny!)
  • a cationic complex is first produced by the addition of a silver salt by abstraction of the chloride ion.
  • this cationic complex inserts, for example, a molecule of vinyl acetate and thus forms a complex of the formula II.
  • Another component of the present invention is a process for the polymerization of vinyl esters using the catalyst or catalyst system according to the invention, polymerization being understood to mean both the homopolymerization of vinyl esters and the copolymerization of vinyl esters with other olefins.
  • Examples of other olefins are 1-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, ethyl norbomadiene and cyclic olefins such as norbornene, cyclopentadiene, tetracyclododecene or methyl norbomene, and polar monomers such as methyl acrylate, methyl methacrylate, acrylic acid, acrylic acid, acrylic acid -Butyl acrylate and 2-ethylhexyl acrylate.
  • Vinyl acetate is preferably homopolymerized in the process according to the invention, or vinyl acetate with one or more 1-olefins having 2 to 8 carbon atoms, such as
  • the polymerization can optionally be carried out either with an additive of the formula III or without an additional additive:
  • M 2 is the same or different and is a metal of the 1st to 14th group of the
  • Periodic table is, 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 additives of the formula III optionally used according to the invention are one or more compounds of the type of an aluminoxane and / or another Lewis acid.
  • the polymerization is carried out at a temperature of from -20 to 300 ° C., preferably from 0 to
  • the polymerization can be carried out in solution, in bulk, in suspension or in emulsion, continuously or batchwise, in one or more stages.
  • Suitable solvents for the polymerization are, for example, aliphatic hydrocarbons such as pentane,
  • the cocatalyst of the formula III which together with at least one compound of the formula I or formula II according to the invention can form the catalyst system, contains at least one compound of the aluminoxane or Lewis acid type.
  • cocatalysts which can form the catalyst system together with a compound of the formula I or formula II are: aluminoxanes, for example in JACS 117 (1995), 6465-74 and Organometallics 13 (1994), 2957-2969 are described, or Lewis acids, which consist, for example, of boron or organoaluminium compounds, or cocatalysts, which are described in EP-A-924223, DE-A-19622207, EP-A-601830, EP-A-824112, EP-A -8241 13, EP-A-81 1627, WO97 / 1 1775 and DE-A-19606167.
  • Lewis acids are those which contain at least one or more atoms of lithium, magnesium, scandium, titanium, boron, aluminum, silicon and / or tin. It is particularly preferred to use at least one organoboron or organoaluminum compound which contains C1-C20 carbon-containing groups, such as branched or unbranched alkyl or
  • Haloalkyl such as 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 (trifluoromethyl) phenyl.
  • 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 (trifluoromethyl) phenyl.
  • aryl or haloaryl such as phenyl, to
  • Tris (3,5-difluorophenyl) borane Tris (3,5-difluorophenyl) borane, tris (4-fluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (tolyl) borane, tris (3,5-dimethylphenyl) 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
  • polar polymers such as. e.g. Polyurethanes, polymethacrylates, polymethyl methacrylates, polyvinyl acetate, polyacrylonitrile, polyethylene glycol or copolymers).
  • Suitable inorganic oxides can be found in the II. VI. Main group of the
  • Periodic table and the lll.-IV. Subgroup of the Periodic Table of the Elements examples include silicon dioxide, hydrotalcite, aluminum oxide, and mixed oxides of the elements calcium, aluminum, silicon, magnesium, titanium and corresponding oxide mixtures.
  • 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.

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  • 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 des composés d'un genre nouveau, pouvant s'utiliser comme catalyseurs dans la polymérisation et la copolymérisation de vinylesters. L'invention concerne en outre un procédé de polymérisation et de copolymérisation de vinylesters, à l'aide desdits composés.
PCT/EP2003/012538 2002-11-20 2003-11-11 Catalyseurs de metal de transition pour produire des polyvinylesters WO2004046209A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2002154093 DE10254093A1 (de) 2002-11-20 2002-11-20 Übergangsmetall-Katalysatoren zur Herstellung von Polyvinylestern
DE10254093.4 2002-11-20

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WO2004046209A1 true WO2004046209A1 (fr) 2004-06-03

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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)

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