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WO2000047634A1 - Production de polymeres vinyliques - Google Patents

Production de polymeres vinyliques Download PDF

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Publication number
WO2000047634A1
WO2000047634A1 PCT/GB2000/000324 GB0000324W WO0047634A1 WO 2000047634 A1 WO2000047634 A1 WO 2000047634A1 GB 0000324 W GB0000324 W GB 0000324W WO 0047634 A1 WO0047634 A1 WO 0047634A1
Authority
WO
WIPO (PCT)
Prior art keywords
mixture
transition metal
alkyl
oxidation state
halogen
Prior art date
Application number
PCT/GB2000/000324
Other languages
English (en)
Inventor
Derek John Irvine
Christopher David Borman
Original Assignee
Ineos Acrylics Uk Ltd.
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 Ineos Acrylics Uk Ltd. filed Critical Ineos Acrylics Uk Ltd.
Priority to AU23078/00A priority Critical patent/AU2307800A/en
Publication of WO2000047634A1 publication Critical patent/WO2000047634A1/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
    • C08F4/00—Polymerisation catalysts
    • 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
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols

Definitions

  • the present invention concerns the production of vinylic polymers, especially, but not limited to, acrylic polymers, for example methacrylate and acrylate copolymers and homopolymers, using atom transfer radical polymerisation.
  • Atom transfer radical polymerisation of unsaturated monomers such as styrene and methyl methacrylate has been reported by Matyjaszewski et al (J. Am. Chew. Soc. , (1995), 117, 5614; J. Am. Chem. Soc , (1997), 119, 674; Macromolecules, (1998), 31 , 1 527) and Haddleton et al (Macromolecules, (1997), 30, 2190; Macromolecules, (1997), 30, 3992).
  • the alkyl radical then adds to the monomer in a chain reaction which may be terminated by the addition of an abstracted halogen back from the metal complex. Subsequent removal of the halogen may then lead to further addition of monomer.
  • This mode of polymerisation is controlled and normally leads to halogen-terminated polymer of narrow molecular weight distribution in which the molecular weight is dependent upon the concentration of initiator used.
  • the present invention provides an ATRP process which differs from the standard process.
  • the at least one vinylic monomer preferably comprises an acrylic monomer such as an alkyl acrylate, alkyl (alkyl)acrylate or acrylic or (alkyl)acrylic acid.
  • Preferred monomers include optionally functionalised alkyl acrylates and alkyl methacrylates, especially, methyl methacrylate (MMA), ethyl methacrylate, n-propyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, hydroxyethyl methacrylate, ethyl acrylate, butyl acrylate, methyl acrylate.
  • Other suitable monomers include styrene (including substituted or functionalised styrenes) acrylonitrile and other vinylic species, e.g. vinyl acetate.
  • the transition metal which forms a complex or precursor thereof, wherein the transition metal in a first oxidation state is reversibly capable of bonding to a halogen atom X and entering a second oxidation state may be selected from e.g. copper, nickel, iron or ruthenium but is preferably copper.
  • the transition metal complex may be any of those which have been found suitable for use in ATRP reactions of vinylic monomers, e.g. as described in the literature references supra.
  • the transition metal complex preferably comprises Cu-L n , where L is a ligand which is preferably a substituted pyridine compound, especially 2,2'- bipyridine or a substituted analogue thereof.
  • transition metal complexes include Ru(PPh 3 ) 3 CI 2 as described by Sawamoto et al (Macromolecules (1995) 28 1721 - 1723).
  • the initiator is a halogen-containing compound R-X.
  • the halogen X is preferably Cl or Br.
  • Suitable initiator compounds include alkyl and aryl halides and other organic haiide compounds such as ethyl-2-bromoisobutyrate, 1-phenyiethyl bromide, 1-phenylethyl chloride, p-toluenesulphonyl chloride, benzhydryl chloride, 1,1,1-trichloroacetone, ⁇ , ⁇ -dichloroacetophenone, carbon tetrachloride.
  • organic haiide compounds such as ethyl-2-bromoisobutyrate, 1-phenyiethyl bromide, 1-phenylethyl chloride, p-toluenesulphonyl chloride, benzhydryl chloride, 1,1,1-trichloroacetone, ⁇ , ⁇ -dichloroacetophenone, carbon tetrachloride.
  • Lewis acids include aluminium complex compounds, metal halides, e.g. Zinc halides, lithium halides, iron trichloride, boron trifluoride, acetyl acetonate (Acac), conjugated organic acids and other organic acids such as camphorsulfonic acid.
  • a preferred aluminium compound is methyl aluminium bis (2,6-di-tert-butyl-4-methyl) phenoxide.
  • the Lewis acid should be soluble in the reaction medium.
  • the reaction rate may be increased to the extent that the reaction solution becomes viscous much more quickly than in the absence of such a compound.
  • control over the polydispersity of the polymer produced may be adversely affected, possibly because of the impaired mobility of the polymer chains, and/ or other reactant or intermediate species present.
  • We have found that the detrimental effects of a rapid rise in the viscosity of the reaction mixture may be overcome to a large extent by the addition of solvent to the reaction mixture as the reaction progresses.
  • the amount of chain transfer agent added to the reaction mixture varies according to the type of substance used and its mode of action. If a catalytic chain transfer agent (CCT) is used, we have found that the optimum properties of the resulting polymer are achieved when the CCT is present at a level of 3 - 30, more preferably 5 - 15, especially about 10 ppm by weight based on the total weight of the reaction mixture, including solvent.
  • CCT catalytic chain transfer agent
  • a mercaptan it is preferably present at a molar concentration of active sites approximately equal to the molar concentration of the initiator used. This is because each initiator molecule may initiate one chain and each mercaptan group may terminate one chain.
  • the reaction mixture may contain other additives which are used to change the properties of the polymer, e.g. impact-modifying materials, colourants, processing aids etc.
  • the PMMA produced in this way was isolated by resuspension of the reaction mixture in tetrahydrofuran (Fisher) followed by filtration through a small column of alumina
  • This reaction used o-xylene as a solvent and the reaction was done at a temperature of 120 °C

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerization Catalysts (AREA)

Abstract

L'invention porte sur un procédé de production d'un polymère acrylique par polymérisation radicalaire de transfert d'atome (ATRP). Ce procédé consiste à (i) former un mélange d'au moins un monomère vinylique, un complexe de métaux de transition ou un précurseur de ceux-ci, le métal de transition dans un premier état d'oxydation pouvant se lier de manière réversible à un atome d'halogène X et introduire un second état d'oxydation; (ii) ajouter à ce mélange un amorceur R-X, X représentant halogène et R un alkyle, un alkyle substitué ou un groupe carbone halogéné de sorte que le monomère acrylique soit polymérisé par polymérisation radicalaire de transfert d'atome. Ce procédé se caractérise en ce que le mélange de l'étage (i) comprend également un acide de Lewis soluble dans le mélange de réaction. Ce procédé permet d'obtenir des réactions plus rapides que les procédés ATRP traditionnels.
PCT/GB2000/000324 1999-02-08 2000-02-07 Production de polymeres vinyliques WO2000047634A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU23078/00A AU2307800A (en) 1999-02-08 2000-02-07 Production of vinylic polymers

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9902564.5 1999-02-08
GBGB9902564.5A GB9902564D0 (en) 1999-02-08 1999-02-08 Production of vinylic polymers

Publications (1)

Publication Number Publication Date
WO2000047634A1 true WO2000047634A1 (fr) 2000-08-17

Family

ID=10847157

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2000/000324 WO2000047634A1 (fr) 1999-02-08 2000-02-07 Production de polymeres vinyliques

Country Status (3)

Country Link
AU (1) AU2307800A (fr)
GB (1) GB9902564D0 (fr)
WO (1) WO2000047634A1 (fr)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003020774A1 (fr) * 2001-09-03 2003-03-13 Basf Aktiengesellschaft Procede de production d'un produit de reaction polymere par catalyse par metal
WO2003031481A2 (fr) * 2001-10-12 2003-04-17 Carnegie Mellon University Amorçage inverse et normal simultane d'une polymerisation radicalaire par transfert d'atome (atrp)
US7064166B2 (en) * 2001-10-12 2006-06-20 Carnegie Mellon University Process for monomer sequence control in polymerizations
US7795355B2 (en) 2004-03-05 2010-09-14 Carnegie Mellon University Preparation of functional polymers
US7893174B2 (en) 2004-03-05 2011-02-22 Carnegie Mellon University Atom transfer radical polymerization process
US7893173B2 (en) 2005-08-26 2011-02-22 Carnegie Mellon University Polymerization process with catalyst reactivation
US8252880B2 (en) 2007-05-23 2012-08-28 Carnegie Mellon University Atom transfer dispersion polymerization
US8273823B2 (en) 2005-08-23 2012-09-25 Carnegie Mellon University Atom transfer radical polymerization in microemulsion and true emulsion polymerization processes
US8367051B2 (en) 2006-10-09 2013-02-05 Carnegie Mellon University Preparation of functional gel particles with a dual crosslink network
US8865797B2 (en) 2007-05-23 2014-10-21 Carnegie Mellon University Hybrid particle composite structures with reduced scattering
US8962764B2 (en) 2009-03-27 2015-02-24 Carnegie Mellon University Preparation of functional star macromolecules
US9533297B2 (en) 2012-02-23 2017-01-03 Carnegie Mellon University Ligands designed to provide highly active catalyst complexes
US9644042B2 (en) 2010-12-17 2017-05-09 Carnegie Mellon University Electrochemically mediated atom transfer radical polymerization
US9982070B2 (en) 2015-01-12 2018-05-29 Carnegie Mellon University Aqueous ATRP in the presence of an activator regenerator
US10072042B2 (en) 2011-08-22 2018-09-11 Carnegie Mellon University Atom transfer radical polymerization under biologically compatible conditions
US11174325B2 (en) 2017-01-12 2021-11-16 Carnegie Mellon University Surfactant assisted formation of a catalyst complex for emulsion atom transfer radical polymerization processes

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5763548A (en) * 1995-03-31 1998-06-09 Carnegie-Mellon University (Co)polymers and a novel polymerization process based on atom (or group) transfer radical polymerization
EP0872493A2 (fr) * 1997-04-14 1998-10-21 Case Western Reserve University Procédé de polymérisation d'acrylonitrile

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5763548A (en) * 1995-03-31 1998-06-09 Carnegie-Mellon University (Co)polymers and a novel polymerization process based on atom (or group) transfer radical polymerization
EP0872493A2 (fr) * 1997-04-14 1998-10-21 Case Western Reserve University Procédé de polymérisation d'acrylonitrile

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 132, Columbus, Ohio, US; abstract no. 166605, GUO, JIANHUA ET AL: "Catalytic system including Al(OiPr)3 as a promoter for atom transfer radical polymerization" XP002138470 *
GAOFENZI XUEBAO (1999), (6), 725-730 *

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003020774A1 (fr) * 2001-09-03 2003-03-13 Basf Aktiengesellschaft Procede de production d'un produit de reaction polymere par catalyse par metal
WO2003031481A2 (fr) * 2001-10-12 2003-04-17 Carnegie Mellon University Amorçage inverse et normal simultane d'une polymerisation radicalaire par transfert d'atome (atrp)
WO2003031481A3 (fr) * 2001-10-12 2003-11-06 Univ Carnegie Mellon Amorçage inverse et normal simultane d'une polymerisation radicalaire par transfert d'atome (atrp)
US6759491B2 (en) 2001-10-12 2004-07-06 Carnegie Mellon University Simultaneous reverse and normal initiation of ATRP
US7064166B2 (en) * 2001-10-12 2006-06-20 Carnegie Mellon University Process for monomer sequence control in polymerizations
US8404788B2 (en) 2004-03-05 2013-03-26 Carnegie Mellon University Atom transfer radical polymerization process
US7795355B2 (en) 2004-03-05 2010-09-14 Carnegie Mellon University Preparation of functional polymers
US7893174B2 (en) 2004-03-05 2011-02-22 Carnegie Mellon University Atom transfer radical polymerization process
US8273823B2 (en) 2005-08-23 2012-09-25 Carnegie Mellon University Atom transfer radical polymerization in microemulsion and true emulsion polymerization processes
US7893173B2 (en) 2005-08-26 2011-02-22 Carnegie Mellon University Polymerization process with catalyst reactivation
US8367051B2 (en) 2006-10-09 2013-02-05 Carnegie Mellon University Preparation of functional gel particles with a dual crosslink network
US8252880B2 (en) 2007-05-23 2012-08-28 Carnegie Mellon University Atom transfer dispersion polymerization
US8865797B2 (en) 2007-05-23 2014-10-21 Carnegie Mellon University Hybrid particle composite structures with reduced scattering
US8962764B2 (en) 2009-03-27 2015-02-24 Carnegie Mellon University Preparation of functional star macromolecules
US9644042B2 (en) 2010-12-17 2017-05-09 Carnegie Mellon University Electrochemically mediated atom transfer radical polymerization
US10072042B2 (en) 2011-08-22 2018-09-11 Carnegie Mellon University Atom transfer radical polymerization under biologically compatible conditions
US9533297B2 (en) 2012-02-23 2017-01-03 Carnegie Mellon University Ligands designed to provide highly active catalyst complexes
US9982070B2 (en) 2015-01-12 2018-05-29 Carnegie Mellon University Aqueous ATRP in the presence of an activator regenerator
US11174325B2 (en) 2017-01-12 2021-11-16 Carnegie Mellon University Surfactant assisted formation of a catalyst complex for emulsion atom transfer radical polymerization processes

Also Published As

Publication number Publication date
AU2307800A (en) 2000-08-29
GB9902564D0 (en) 1999-03-24

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