Studies on atom transfer radical polymerization of acrylates and styrenes with controlled polymeric block structures

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dc.contributor Aalto-yliopisto fi
dc.contributor Aalto University en
dc.contributor.author Ibrahim, Khalid
dc.date.accessioned 2012-02-17T07:47:20Z
dc.date.available 2012-02-17T07:47:20Z
dc.date.issued 2006-06-20
dc.identifier.isbn 951-22-8249-6
dc.identifier.issn 1795-4584
dc.identifier.uri https://aaltodoc.aalto.fi/handle/123456789/2716
dc.description.abstract Atom transfer radical polymerization (ATRP) was applied to homo and block copolymerization of vinyl monomers methacrylates, acrylates, and styrene with iron (FeCl2.4H2O) as the transition metal in most cases. As complexing ligand either a commercially available ligand (triphenyl phosphine) (PPh3) or synthetic aliphatic amines were used. As initiators, methyl 2-bromopropionate, ethyl 2-bromoisobutyrate, α,α-dichloroacetophenone, and poly(ethylene oxide) macroinitiator were employed. Block copolymerization of n-butyl methacrylate-b-tert-butyl acrylate (BMA-b-tBA) was performed by two-step ATRP method. The results showed that, for well-defined copolymers, a low conversion macroinitiator (conversion 35%) is preferable to a high conversion one. Four tetradentate nitrogen ligands, viz. dichloro{[N,N'-diphenyl-N,N'-di(quinoline-2-methyl)]-1,2-ethylene diamine} (1), {[N,N'-dioctyl-N,N'-di(quinoline-2-methyl)]-1,2-ethylene diamine} (2), {[N,N'-dibenzyl-N,N'-di(quinoline-2-methyl)]-1,2-ethylene diamine} (3), and (1R,2R)-(-)-N,N'-di(quinoline-2-methyl)diiminocyclohexane (4), were synthesised at the University of Helsinki, and used as complexing ligands in iron-mediated polymerization of methyl methacrylate. High to moderate conversions (87%, 43%) were obtained in relatively short times (90 min for 1 and 30 min for 2), which indicates an efficient catalyst system. When the bulkiness of the substituents was significantly increased, as in ligand 3, polymerization rate was decreased and control was lost. Ligand 4 was less efficient than the other ligands, probably because the ethylene bridge was replaced by cyclohexane bridge. Poly(ethylene oxide) monochloro macroinitiators and poly(ethylene oxide) telechelic macroinitiators (Cl-PEO-Cl) were prepared from monohydroxy functional and dihydroxy functional poly(ethylene oxide) in the presence of 2-chloro propionyl chloride and applied to the polymerization of styrene (S) or methyl methacrylate (MMA). The polymerization of styrene was carried out in bulk at 140 °C and catalysed by copper(I) chloride (CuCl) in the presence of 2,2' -bipyridine (bipy) ligand (CuCl/ bipy), but the polymerization of MMA was carried out in the presence of (FeCl2.4H2O)/ (PPh3) catalytic system. With most of the macroinitiators, the living nature of the polymerizations led to block copolymers with narrow molecular weight distribution (Mw/Mn < 1.3). Adjustment of the content of the PEO blocks (>90% by mass) allowed the preparation of water-soluble/water-dispersible block copolymers. Small amounts of the PEO-PS-based block copolymers were applied to modify the paper surface. Chain length of the hydrophilic block and/or the amount of hydrophobic block was found to play an important role in modification of the paper surface. It was also found that water-dispersible triblock copolymer containing 10 wt-% PS makes the paper surface highly hydrophobic (contact angle >115° ) and retards water absorption on both light weight coated base paper (LWC) and fine base paper (FP). The effect on oil absorption was less significant. en
dc.format.extent 56, [59]
dc.format.mimetype application/pdf
dc.language.iso en en
dc.publisher Helsinki University of Technology en
dc.publisher Teknillinen korkeakoulu fi
dc.relation.ispartofseries TKK dissertations en
dc.relation.ispartofseries 34 en
dc.relation.haspart Ibrahim, K., Löfgren, B., and Seppälä, J., Towards more controlled poly(n-butyl methacrylate) by atom transfer radical polymerization, European Polymer Journal 39, 939-944 (2003). [article1.pdf] © 2003 Elsevier Science. By permission.
dc.relation.haspart Ibrahim, K., Löfgren, B., and Seppälä, J., Synthesis of tertiary-butyl acrylate polymers and preparation of diblock copolymers using atom transfer radical polymerization, European Polymer Journal 39, 2005-2010 (2003). [article2.pdf] © 2003 Elsevier Science. By permission.
dc.relation.haspart Ibrahim, K., Yliheikkilä, K., Abu-Surrah, A., Löfgren, B., Lappalainen, K., Leskelä, M., Repo, T., and Seppälä, J., Polymerization of methyl methacrylate in the presence of iron(II) complex with tetradentate nitrogen ligands under conditions of atom transfer radical polymerization, European Polymer Journal 40, 1095-1104 (2004). [article3.pdf] © 2004 Elsevier Science. By permission.
dc.relation.haspart Ibrahim, K., Starck, P., Löfgren, B., and Seppälä, J., Synthesis and characterization of amphiphilic triblock copolymers by iron-mediated atom transfer radical polymerization, Journal of Polymer Science Part A: Polymer Chemistry 43, 5049-5061 (2005). [article4.pdf] © 2005 by authors and © 2005 John Wiley & Sons. By permission.
dc.relation.haspart Ibrahim, K., Salminen, A., Holappa, S., Kataja, K., Lampinen, H., Löfgren, B., Laine, J., and Seppälä, J., Preparation and characterization of polystyrene-poly(ethylene oxide) amphiphilic block copolymers via ATRP: potential application as paper coating materials, Journal of Applied Polymer Science, accepted for publication. [article5.pdf] © 2006 by authors and © 2006 John Wiley & Sons. By permission.
dc.subject.other Chemistry en
dc.title Studies on atom transfer radical polymerization of acrylates and styrenes with controlled polymeric block structures en
dc.type G5 Artikkeliväitöskirja fi
dc.description.version reviewed en
dc.contributor.department Department of Chemical Technology en
dc.contributor.department Kemian tekniikan osasto fi
dc.subject.keyword atom transfer radical polymerization en
dc.subject.keyword catalyst en
dc.subject.keyword controlled en
dc.subject.keyword macroinitiator en
dc.subject.keyword coating en
dc.subject.keyword paper surface en
dc.identifier.urn urn:nbn:fi:tkk-007030
dc.type.dcmitype text en
dc.type.ontasot Väitöskirja (artikkeli) fi
dc.type.ontasot Doctoral dissertation (article-based) en
dc.contributor.lab Laboratory of Polymer Technology en
dc.contributor.lab Polymeeriteknologian laboratorio fi


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