WO2000053642A1 - (co)polymerisation controlee par des systemes complexes de metal/n-heterocycles - Google Patents

(co)polymerisation controlee par des systemes complexes de metal/n-heterocycles Download PDF

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Publication number
WO2000053642A1
WO2000053642A1 PCT/EP2000/001782 EP0001782W WO0053642A1 WO 2000053642 A1 WO2000053642 A1 WO 2000053642A1 EP 0001782 W EP0001782 W EP 0001782W WO 0053642 A1 WO0053642 A1 WO 0053642A1
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WO
WIPO (PCT)
Prior art keywords
dimethyl
bipyridine
initiator
mixtures
derivatives
Prior art date
Application number
PCT/EP2000/001782
Other languages
German (de)
English (en)
Inventor
Ulrich S. Schubert
Georg Hochwimmer
Christian Spindler
Oskar Nuyken
Original Assignee
Schubert Ulrich S
Georg Hochwimmer
Christian Spindler
Oskar Nuyken
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 Schubert Ulrich S, Georg Hochwimmer, Christian Spindler, Oskar Nuyken filed Critical Schubert Ulrich S
Priority to AU34265/00A priority Critical patent/AU3426500A/en
Publication of WO2000053642A1 publication Critical patent/WO2000053642A1/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
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation

Definitions

  • the present invention relates to a process for the preparation of homo-, co- and block copolymers by controlled polymerization using N-heterocycle-metal complexes.
  • ATRP atom transfer radical polymerization
  • the object of the present invention is a process for the production of colorless or predominantly colorless homo-, co- and block copolymers based on free-radically polymerized monomers such as styrene and / or arylates with low metal ion concentrations.
  • the present invention therefore relates to a process which is characterized in that an initiator and a complex or a complex mixture in solution or as a solid which consists of a transition metal ion is added to carry out the polymerization of free-radically polymerizable monomers selected from Cu (II), Fe (II), Ni (II), Ru (II), Co (II), Zn (II), Mn (II) or Pd (II) and bi- or multidentate ligands or Mixtures of these, the ligand containing at least one heteroatom and to the. Via at least one heteroatom
  • Transition metal ion is bound, and composed of any anion.
  • bipyridines for example and preferably 4,4'-dimethyl-2,2'-bipyridine, 5,5'-dimethyl-2,2'-bipyridine, 6,6'-dimethyl
  • ligands -2,2'-bipyridine, 5,6'-dimethyl-2,2'-bipyridine, 4,6'-dimethyl-2,2'-bipyridine, 4,5'-dimethyl-2,2'-bipyridine, or their derivatives
  • variously substituted or functionalized terpyridines for example and preferably 5.5 "-dimethyl-2,2 ': 6', 2" -terpyridine, 6.6 "-dimethyl-2,2 ': 6', 2" -terpyridine, 4,4 "-dimethyl-2, 2 ': 6', 2 "-Te ⁇ yridin, or their derivatives
  • analogues such as and preferably Quate ⁇ yridine or 4,6-bis
  • PF 6 , SbFg, CIO4 etc. can be used, for example, and preferably as anions.
  • Suitable initiators are organic compounds with any one or more leaving groups Y.
  • Organic compounds are to be understood as meaning compounds with aliphatic, cycloaliphatic, aromatic or aliphatic-aromatic hydrocarbons which can contain at least one heteroatom.
  • the leaving group Y is not critical and can be chosen arbitrarily.
  • Y is preferably a halide, cyanide (CN), tosylate, mesylate, triflate or any other leaving group.
  • Preferred initiators are compounds of the formulas (I), (II), (III) and (IV):
  • R 1 , R 2 and R 3 independently of one another are hydrogen, any saturated or unsaturated aliphatic or cycloaliphatic hydrocarbons which can contain at least one hetero atom, or any saturated or unsaturated heterocyclic systems and
  • R 1 , R 2 and R 3 are preferably independently of one another hydrogen, aliphatic or cycloaliphatic or aromatic-aliphatic hydrocarbons with preferably 1 to 20 carbon atoms, which can be substituted with, for example, halogen, alkoxy and heteroatoms, such as oxygen or nitrogen - can hold.
  • R 1 , R 2 and R 3 are particularly preferably substituted or unsubstituted phenyl, naphthyl, pyridyl, phenylalkyl, naphthylalkyl, halogen, alkyl, alkoxy, etc. being preferred as substituents.
  • Phenylalkyl halide with preferably 1 to 4 carbon atoms in the alkyl is very particularly preferred. Phenylethyl halide is particularly suitable.
  • the complex can be dissolved or suspended directly in the monomer or in an additional solvent, e.g. Acetonitrile, dissolved or suspended.
  • additional solvent e.g. Acetonitrile
  • the polymerization can thus be carried out in bulk, with small amounts of solvent or in solution.
  • the process according to the invention leads to poly (styrenes), poly (methacrylates) or poly (acr lates) and their derivatives or copolymers or block copolymers thereof with polydipersities down to 1.08 (determined by means of gel permeation Chromatography in chloroform on Shodex GPC K-802S columns, Waters Liquid Chromatograph System, Waters Differential Refractometer 410, polystyrene standards).
  • the polymerization temperatures are generally 40 to 200, preferably
  • a Lewis acid is added for the polymerization (such as Al (iOPr) 3 , Al alkyls or other Al alcoholates or Al alcoholates formed in situ or formed during the polymerization).
  • This Lewis acid can also be dispensed with at polymerization temperatures above 80 ° C.
  • Ratios (compared to the monomer) are used.
  • the molar masses obtained can be adjusted within a wide range by the concentration ratio of the compound with leaving group (e.g. 1-phenylethyl bromide) to the monomer concentration.
  • Any copolymer can be obtained by polymerizing mixtures of two or more different monomers.
  • Block copolymers can be obtained (polydispersities between 1J0 and 1.25 can be achieved).
  • the process according to the invention is characterized in that the polymers produced (molar masses up to a few 10000 g / mol) after falling over in
  • Methanol can be isolated directly as colorless materials.
  • the metal content is well below 250 ppm (determined by means of UV / Vis spectroscopy and atomic absorption spectroscopy).
  • the molar masses of the polymer samples obtained were determined by means of gel permeation chromatography. Depending on the reaction time, they were 13,000 to 50,000 g / mol at one Polydispersity of the molar masses (M w / M n ) between 1.2 to 2.4. A conversion of 50% was achieved after 31 hours.
  • the molar masses of the polymer samples obtained were determined by means of gel permeation chromatography. Depending on the reaction time, they were 1000 to 6000 g / mol with a polydispersity of the molar masses (M w / M n ) between 1.2 and 1.9. The conversion after 30 hours was 30%.

Abstract

L'invention concerne un procédé permettant de procéder à une (co)polymérisation contrôlée de monomères radicalement polymérisables, par exemple du styrène, du méthacrylate ou de l'acrylate et leurs dérivés, à l'aide d'un système initiateur/catalyseur à base d'un composé ayant au moins un groupe de départ, des complexes de métal/N-hétérocycles de la formule [MLn]m+(A), (où M = Cu(II), Cu(I), Fe(II) etc. et des ions antagonistes quelconques, (A)) et éventuellement d'acides de Lewis et/ou de solvants. Le procédé se distingue notamment par l'obtention de polymères incolores ayant de faibles concentrations d'ions métalliques résiduels et la bonne aptitude de réglage des masses molaires liée à des polydispersités relativement faibles.
PCT/EP2000/001782 1999-03-05 2000-03-02 (co)polymerisation controlee par des systemes complexes de metal/n-heterocycles WO2000053642A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU34265/00A AU3426500A (en) 1999-03-05 2000-03-02 Controlled (co)polymerisation with n-heterocycles metal complex systems

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19909624 1999-03-05
DE19909624.4 1999-03-05

Publications (1)

Publication Number Publication Date
WO2000053642A1 true WO2000053642A1 (fr) 2000-09-14

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2000/001782 WO2000053642A1 (fr) 1999-03-05 2000-03-02 (co)polymerisation controlee par des systemes complexes de metal/n-heterocycles

Country Status (2)

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AU (1) AU3426500A (fr)
WO (1) WO2000053642A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4424359A (en) * 1980-07-17 1984-01-03 Ciba-Geigy Corporation Vinyl-substituted 2,2'-bipyridine compounds
GB2321247A (en) * 1997-01-20 1998-07-22 Courtaulds Plc Polymerisation reactions
US5807937A (en) * 1995-11-15 1998-09-15 Carnegie Mellon University Processes based on atom (or group) transfer radical polymerization and novel (co) polymers having useful structures and properties

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4424359A (en) * 1980-07-17 1984-01-03 Ciba-Geigy Corporation Vinyl-substituted 2,2'-bipyridine compounds
US5807937A (en) * 1995-11-15 1998-09-15 Carnegie Mellon University Processes based on atom (or group) transfer radical polymerization and novel (co) polymers having useful structures and properties
GB2321247A (en) * 1997-01-20 1998-07-22 Courtaulds Plc Polymerisation reactions

Also Published As

Publication number Publication date
AU3426500A (en) 2000-09-28

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