We describe here a new strategy for the synthesis of polymers with highly branched architectures. The strategy involves the synthesis by anionic polymerization of well-defined AB2 polystyrene (condensation) macromonomers with molecular weights from 3500 to 38 000 g mol-1, which are then converted via a one-pot polycondensation reaction into high-molecular-weight, long-chain (hyper)branched architectures. Because the hyperbranched structures are built up from condensation macromonomers, we have coined the term “HyperMac” to describe these branched polymers. In this paper, we report the synthesis of the macromonomers, the optimal conditions for the polycondensation reaction, and some preliminary characterization studies.

. (2006) 'DendriMacs : well-dened dendritically branched polymers synthesized by an iterative convergent strategy involving the coupling reaction of AB2 macromonomers. ', Macromolecules., 39 (6). pp. 2144-2152. Further information on publisher's website:http://dx.doi.org/10.1021/ma052627dPublisher's copyright statement:This document is the Accepted Manuscript version of a Published Work that appeared in nal form in Macromolecules, copyright c American Chemical Society after peer review and technical editing by the publisher. To access the nal edited and published work see http://pubs.acs.org/doi/abs/10.1021/ma052627d. Additional information:Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. ABSTRACT. We describe here the first example of an iterative convergent strategy for the synthesis of dendritically branched polymers involving condensation coupling reactions of AB 2 macromonomers.The macromonomers were synthesized by living anionic polymerization, initiated with 3-tertbutyldimethylsiloxy-1-propyllithium and end capped with 1,1-bis(4-tert-butyldimethylsiloxyphenyl)ethylene. Following a deprotection reaction, the macromonomer, functionalized with two phenol groups and one primary alcohol group, can be built up into a dendritic structure by a series of Williamson coupling reactions and subsequent end group modification reactions. Since the Dendritic structures are built up from Macromonomers we have coined the term 'DendriMac' to describe these branched 2 polymers. In this paper we will discuss the synthesis of the macromonomer, the iterative reaction sequence and merits of a convergent strategy. Some preliminary characterization data will also be reported.

Summary:We describe here a new strategy for the synthesis of polymers with highly branched architectures. The strategy involves the synthesis by anionic polymerization of well-defined AB 2 polystyrene macromonomers with molecular weights from 3,600 to 94,000 gmol À1 , which are then converted via a one-pot polycondensation reaction into high molecular weight, long-chain (hyper)branched architectures. Since the Hyperbranched structures are built up from condensation Macromonomers we have coined the term 'HyperMac' to describe these branched polymers. In this paper we report the synthesis of the HyperMacs, the optimal conditions for the polycondensation reaction and some preliminary characterization studies.

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