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Atom transfer radical polymerization of methyl acrylate from a multifunctional initiator at ambient temperature
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.ORCID iD: 0000-0002-8194-0058
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.ORCID iD: 0000-0002-8348-2273
2002 (English)In: Polymer, ISSN 0032-3861, E-ISSN 1873-2291, Vol. 43, no 15, 4237-4242 p.Article in journal (Refereed) Published
Abstract [en]

A multifunctional initiator for ATRP has been synthesized by reacting a hyperbranched polyether, based on 3-ethyl-3-(hydroxymethyl)oxetane, with 2-bromo-isobutyrylbromide. The macroinitiator contained approximately 25 initiating sites per molecule. It was used for the atom transfer radical polymerization of methyl acrylate mediated by Cu(I)Br and tris(2-(dimethylamino)ethyl)amine (Me-6-TREN) in ethyl acetate at room temperature. This yielded a co-polymer with a dendritic-linear architecture. The large number of growing chains from each macromolecule increases the probability of inter-and intramolecular reactions. In order to control these kinds of polymerizing systems and prevent them from forming a gel, the concentration of propagating radicals must be kept low. The polymerizations under these conditions were well controlled. When a ratio of initiating sites-to-catalyst of 1:0.05 was used, the polymers from all of the reactions had a low polydispersity, ranging from 1.1 to 1.4. None of the polymerizations under these conditions gave gelation. Monomer conversions as high as 65% were reached while maintaining control over the polymerization. (C) 2002 Elsevier Science Ltd. All rights reserved.

Place, publisher, year, edition, pages
OXFORD, ENGLAND: ELSEVIER SCI LTD , 2002. Vol. 43, no 15, 4237-4242 p.
Keyword [en]
atom transfer radical polymerization, 'living'/controlled radical polymerization, multifunctional initiator, RING-OPENING POLYMERIZATION, STAR POLYMERS, METHACRYLATE, POLYESTERS, POLYSTYRENE, COPOLYMERS, COMPLEXES, SYSTEM, BLOCK
National Category
Polymer Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-13007DOI: 10.1016/S0032-3861(02)00258-6ISI: 000176108400017OAI: oai:DiVA.org:kth-13007DiVA: diva2:320181
Note
QC 20100524 NR 20140804Available from: 2010-05-24 Created: 2010-05-24 Last updated: 2017-12-12Bibliographically approved
In thesis
1. Atom transfer radical polymerization from multifunctional substrates
Open this publication in new window or tab >>Atom transfer radical polymerization from multifunctional substrates
2002 (English)Licentiate thesis, comprehensive summary (Other scientific)
Abstract [en]

Atom transfer radical polymerization (ATRP) has proven to be a powerful technique to obtain polymers with narrow polydispersities and controlled molecular weight. It also offers control over chain-ends. The technique is the most studied and utilized of thecontrolled/”living” radical polymerization techniques since a large number of monomerscan be polymerized under simple conditions. ATRP can be used to obtain polymer graftsfrom multifunctional substrates. The substrates can be either soluble (i. e. based ondendritic molecules) or insoluble (such as gold or silicon surfaces). The large number ofgrowing chains from the multifunctional substrates increases the probability of inter-and intramolecular reactions. In order to control these kinds of polymerizing systems, andsuppress side-reactions such as termination, the concentration of propagating radicalsmust be kept low. To elaborate such a system a soluble multifunctional substrate, based on 3-ethyl-3-(hydroxymethyl)oxetane, was synthesized. It was used as a macroinitiatorfor the atom transfer radical polymerisation of methyl acrylate (MA) mediated byCu(I)Br and tris(2-(dimethylamino)ethyl)amine (Me6-TREN) in ethyl acetate at room temperature. This yielded a co-polymer with a dendritic-linear architecture. Since mostsolid substrates are sensitive to the temperatures at which most ATRP polymerisations are performed, lowering the polymerization temperatures are preferred. ATRP at ambienttemperature is always more desirable since it also suppresses the formation of thermally formed polymer. The macroinitiator contained approximately 25 initiating sites, which well mimicked the conditions on a solid substrate. The polymers had low polydispersity and conversions as high as 65% were reached without loss of control. The solid substrateof choice was cellulose fibers that prior to this study not had been grafted through ATRP.As cellulose fibers a filter paper, Whatman 1, was used due to its high cellulose content.The hydroxyl groups on the surface was first reacted with 2-bromoisobutyryl bromidefollowed by grafting of MA. Essentially the same reaction conditions were used that hadbeen elaborated from the soluble substrate. The grafting yielded fibers that were very hydrophobic (contact angles>100°). By altering the sacrificial initiator-to-monomer ratiothe amount of polymer that was attached to the surface could be tailor. PMA with degreesof polymerization (DP’s) of 100, 200 and 300 were aimed. In order to control that thepolymerizations from the surface was indeed “living” a second layer of a hydrophilicmonomer, 2-hydroxymethyl methacrylate (HEMA), was grafted onto the surface. Thisdramatically changed the hydrophobic behavior of the fibers.

Place, publisher, year, edition, pages
Stockholm: KTH, 2002. 39 p.
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-1447 (URN)
Presentation
(English)
Note
QC 20100524Available from: 2002-06-20 Created: 2002-06-20 Last updated: 2010-05-24Bibliographically approved

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Carlmark, Anna EMalmström Jonsson, Eva

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